Functionalized Olefin Polymers

ABSTRACT

This invention relates to a composition comprising a functionalized C3 to C40 olefin polymer comprising at least 50 mol % of one or more C3 to C40 olefins, and where the olefin polymer, prior to functionalization, has:
         a Dot T-Peel of 1 Newton or more on Kraft paper;   an Mw of 10,000 to 100,000; and   a branching index (g′) of 0.98 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 60,000, or   a branching index of 0.95 or less measured at the Mz of the polymer when the polymer has an Mw of 10,000 to 100,000; and where the C3 to C40 olefin polymer comprises at least 0.001 wt % of a functional group. This invention further relates to blends of such functionalized polymers with other polymers including non-functionalized C3 to C40 olefin polymers as described above.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Pat. No. 7,750,528, which isa continuation-in-part of U.S. Pat. No. 7,524,910, which claims priorityfrom U.S. Ser. No. 60/418,482, filed Oct. 15, 2002 and U.S. Ser. No.60/460,714, filed Apr. 4, 2003. This application is also acontinuation-in-part of U.S. Pat. No. 7,294,681, which claims priorityfrom U.S. Ser. No. 60/418,482, filed Oct. 15, 2002 and U.S. Ser. No.60/460,714, filed Apr. 4, 2003.

FIELD OF THE INVENTION

This invention relates to a composition comprising a functionalizedC3-C40 olefin polymer. This invention further relates to functionalizedolefin polymers, as well as processes to produce and use functionalizedolefin polymers including applications as adhesives, tie layers,primers, compatibility agents, and the like.

BACKGROUND OF THE INVENTION

Olefin based polymers are widely used in various applications due totheir being chemically inert, having low density, and low cost.Applications include adhesives, tie layers, films, fibers, andcombinations thereof.

Olefin based polymers may be formed into various films, which may belaminated to, coated on, or co-extruded with various substrates. Thefilm and the substrate may be combined with other materials to form astructure having a plurality of layers, each layer having a specificpurpose. Packaging laminates, for example, may comprise a plurality oflayers, such as a configurationally rigid core layer of paper orpaperboard, an outer liquid-tight layer, an oxygen gas barrier such as amid-layer of aluminum foil, and/or other layers depending on applicationneeds.

To provide effective adhesion, it is important that good bondingstrength or intimate integrity between the layers be achieved for mostapplications. However, relatively non-polar olefin based polymers do notnormally adhere well to substrates which are more polar.

In addition, the set time of an adhesive may need to be within limitsconsistent with a proposed end use. Tailoring of an adhesive set timehowever may be accomplished at the expense of other attributes of anadhesive. For example, while inclusion of various forms of wax (e.g.,polyethylene wax) may reduce a set time of an adhesive, the inclusion ofa wax may also reduce or destroy adhesive properties in particulartemperature ranges, and/or to particular substrates, especially polarsubstrates.

Adhesives are typically not heat stable, especially with respect tocolor over a period of time when the adhesive is heated at or above itsmelting point. Stability issues related to thermal degradation,including those related to bond strength and color body formation atelevated temperatures, may render various adhesives unfit for a varietyof end uses.

There thus remains a need for an adhesive that will intimately bond toboth polar and non-polar substrates, preferably one that exhibits asuperior durability of bond strength under various temperatureconditions at particular set times and in the presence of aggressiveproducts, and that is heat stable at elevated temperatures.

SUMMARY OF THE INVENTION

This invention relates to a composition comprising a functionalized C3to C40 olefin polymer comprising at least 50 mol % of one or more C3 toC40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraftpaper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of0.98 or less measured at the Mz of the polymer when the polymer has anMw of 10,000 to 60,000, or a branching index (g′) of 0.95 or lessmeasured at the Mz of the polymer when the polymer has an Mw of 10,000to 100,000. This invention further relates to such functionalized C3 toC40 olefin polymers blended with other polymers. In a preferredembodiment the functionalized C3 to C40 olefin polymer is blended withthe same or different non-functionalized C3 to C40 olefin polymercomprising at least 50 mol % of one or more C3 to C40 olefins andhaving: a) a Dot T-Peel of 1 Newton or more on Kraft paper; b) an Mw of10,000 to 100,000; and c) a branching index (g′) of 0.98 or lessmeasured at the Mz of the polymer when the polymer has an Mw of 10,000to 60,000, or a branching index (g′) of 0.95 or less measured at the Mzof the polymer when the polymer has an Mw of 10,000 to 100,000.

By “functionalized C3 to C40 olefin polymer” is meant that the C3 to C40olefin polymer is contacted with a functional group, and optionally acatalyst, heat, initiator, or free radical source to cause all or partof the functional group to incorporate, graft, bond to, physicallyattach to, and or chemically attach to the C3 to C40 olefin polymer. By“functional group” is meant any compound with a weight average molecularweight of 1000 or less that contains a heteroatom and or anunsaturation. Preferably the functional group is a compound containing aheteroatom, such as maleic anhydride. Preferred functional groupsinclude organic acids, organic amides, organic amines, organic esters,organic anhydrides, organic alcohols, organic acid halides (such as acidchlorides, acid bromides, etc.) organic peroxides, and the like.

For ease of reference the functionalized C3 to C40 olefin polymer may beabbreviated as F-POA and a C3 to C40 olefin polymer that has NOT beenfunctionalized may be referred to as a POA.

DETAILED DESCRIPTION

For the purposes of this invention and the claims thereto and for easeof reference, when a polymer is referred to as comprising an olefin, theolefin present in the polymer is the polymerized form of the olefin.

In a preferred embodiment, this invention relates to a compositioncomprising:

1) 0.5 to 99 weight % (preferably 1 to 75 weight %, more preferably 1.5to 40 weight %, preferably 2 to 20 weight %, preferably 2.5 to 10 weight%) of a functionalized C3 to C40 olefin polymer comprising at least 50mol % of one or more C3 to C40 olefins and having: a) a Dot T-Peel of 1Newton or more on Kraft paper; b) an Mw of 10,000 to 100,000; and c) abranching index (g′) of 0.98 or less measured at the Mz of the polymerwhen the polymer has an Mw of 10,000 to 60,000, or a branching index(g′) of 0.95 or less measured at the Mz of the polymer when the polymerhas an Mw of 10,000 to 100,000.

2) 99 to 1 weight % (preferably 99 to 25 weight %, more preferably 98.5to 60 weight %, preferably 98 to 80 weight %, preferably 97.5 to 90weight %) of one or more additional polymers different from thefunctionalized C3 to C40 olefin polymer,

based upon the weight of the additional polymer(s) and thefunctionalized C3 to C40 olefin polymer.

In a preferred embodiment the additional polymer comprises one or moreC3 to C40 olefin polymer comprising at least 50 mol % of one or more C3to C40 olefins and having: a) a Dot T-Peel of 1 Newton or more on Kraftpaper; b) an Mw of 10,000 to 100,000; and c) a branching index (g′) of0.98 or less measured at the Mz of the polymer when the polymer has anMw of 10,000 to 60,000, or a branching index (g′) of 0.95 or lessmeasured at the Mz of the polymer when the polymer has an Mw of 10,000to 100,000.

In a preferred embodiment this invention relates to a blend comprisingF-POA and between 1 and 90 weight % tackifier, preferably between 5 and75 weight %, more preferably between 10 and 60 weight %, more preferablybetween 15 and 50% of tackifier, based upon the weight of the blend, andbetween 10 and 99 weight % of the F-POA, preferably between 95 and 25weight %, more preferably between 40 and 90 weight %, more preferablybetween 85 and 50% of the F-POA.

In another preferred embodiment this invention relates to a blendcomprising F-POA, POA and between 1 and 90 weight % tackifier,preferably between 5 and 75 weight %, more preferably between 10 and 60weight %, more preferably between 15 and 50% of tackifier, based uponthe weight of the blend, and between 10 and 99 weight % of F-POA andPOA, preferably between 95 and 25 weight %, more preferably between 40and 90 weight %, more preferably between 85 and 50%.

In a preferred embodiment comprising POA and F-POA, the POA and theF-POA may include the same olefin polymer or blend of olefin polymerswhich is/are functionalized to become the F-POA, which are then blendedwith POA. In another embodiment, the olefin polymer or blend of olefinpolymers of the POA may be different from the olefin polymer or blend ofolefin polymers functionalized to become the F-POA. In still anotherembodiment, the olefin polymer or blend of olefin polymers of the POAmay be the exact same olefin polymer or blend of olefin polymers thathas been functionalized to become the F-POA. In yet another embodiment,the F-POA may include functionalized analogs of the exact same olefinpolymer or blend of olefin polymers as is in the POA. Preferably, thePOA comprises the exact same olefin polymer as the F-POA, which has beenfunctionalized with maleic anhydride.

C3 to C40 Olefin Polymers (POA's)

Preferred C3 to C40 olefin polymers (also called “POA's” or “POApolymers”) useful in this invention are those described in U.S. Ser. No.10/686,951, filed Oct. 15, 2003 and U.S. Ser. No. 10/687,508, filed Oct.15, 2003, which are incorporated by reference herein. In particular,pages 23 to 91 of U.S. Ser. No. 10/686,951 and pages 22 to 168 of U.S.Ser. No. 10/687,508 provide specific instruction on how to produce theC3 to C40 olefin polymers useful herein. In general preferred POA'scomprise a polypropylene prepared utilizing two or more catalysts(typically metallocene catalysts), wherein one catalyst is selected asbeing capable of producing essentially atactic polypropylene (aPP), andthe other metallocene catalyst is selected as being capable of producingisotactic polypropylene (iPP) under the polymerization conditionsutilized. Preferably, under the polymerization conditions utilized,incorporation of aPP and iPP polymer chains may occur within thein-reactor blend such that an amount of amorphous polypropylene presentin the POA polymer is grafted to isotactic polypropylene, representedherein as (aPP-g-IPP) and/or such that an amount of isotacticpolypropylene present in the POA polymer is grafted to amorphouspolypropylene, represented herein as (iPP-g-aPP).

Preferred POA's useful in this invention include olefin polymercomprising one or more C₃ to C₄₀ olefins, preferably propylene, and lessthan 50 mole % of ethylene, having:

-   -   a) a Dot T-Peel between 1 Newton and the 10,000 Newtons; and    -   b) a Mz/Mn of 2 to 200; and/or    -   c) an Mw of X and a g′ of Y (measured at the Mz of the polymer)        according to the following Table 1:

TABLE 1 X (Mw) Y (g′) 100,000 or less, preferably 80,000 or less,preferably 0.9 or less, 70,000 or less, more preferably 60,000 or less,more preferably 0.7 preferably 50,000 or less, more preferably 40,000 oror less; less, more preferably 30,000 or less, more preferablypreferably 20,000 or less, more preferably 10,000 or less. between 0.5-In some embodiments X is also at least 7000, more 0.9 preferably 10,000,more preferably at least 15,000. 75,000 or less, preferably 70,000 orless, more preferably 0.92 or less, 60,000 or less, more preferably50,000 or less, more preferably, 0.6 preferably 40,000 or less, morepreferably 30,000 or less, or less; more preferably 20,000 or less, morepreferably 10,000 preferably or less. In some embodiments A is also atleast 1000, between 0.4- preferably at least 2000, more preferably atleast 3000, 0.6- more preferably at least 4000, more preferably at least5000, more preferably at least 7000, more preferably 10,000, morepreferably at least 15,000. 50,000 or less, more preferably 40,000 orless, more 0.95 or less, preferably 30,000 or less, more preferably20,000 or preferably 0.7 less, more preferably 10,000 or less. In someembodi- or less; ments A is also at least 1000, preferably at least2000, preferably more preferably at least 3000, more preferably at leastbetween 0.5- 4000, more preferably at least 5000, more preferably at0.7- least 7000, more preferably 10,000, more preferably at least15,000. 30,000 or less, preferably 25,000 or less, more preferably 0.98or less 20,000 or less, more preferably 15,000 or less, more preferablypreferably 10,000 or less. In some embodiments A is between 0.7- also atleast 1000, preferably at least 2000, more 0.98 preferably at least3000, more preferably at least 4000, more preferably at least 5000, morepreferably at least 7000, more preferably 10,000, more preferably atleast 15,000.

Preferred POA's useful in this invention include olefin polymerscomprising one or more C₃ to C₄₀ olefins, preferably propylene, and lessthan 50 mole % of ethylene, having:

-   -   a) a Dot T-Peel between 1 Newton and 10,000 Newtons; and    -   b) a Mz/Mn of 2 to 200; and    -   c) an Mw between 15,000 and 100,000; and    -   d) a g′<(10⁻¹² Mw²−10⁻⁶ Mw+1.0178).

In an embodiment, the g′ may be 0.9 or less, 0.8 or less, 0.7 or less,0.6 or less, 0.5 or less when measured at the Mz of the polymer.

In another embodiment the POA may have a peak melting point (Tm) between40 and 250° C., or between 60 and 190° C., or between 60 and 150° C., orbetween 80 and 130° C. In some embodiments the peak melting point isbetween 60 and 160° C. In other embodiments the peak melting point isbetween 124-140° C. In other embodiments, the peak melting temperatureis between 40-130° C.

In another embodiment the POA may have a viscosity (also referred to aBrookfield Viscosity or Melt Viscosity) of 90,000 mPa·sec or less at190° C. (as measured by ASTM D 3236 at 190° C.); or 80,000 or less, or70,000 or less, or 60,000 or less, or 50,000 or less, or 40,000 or less,or 30,000 or less, or 20,000 or less, or 10,000 or less, or 8,000 orless, or 5000 or less, or 4000 or less, or 3000 or less, or 1500 orless, or between 250 and 6000 mPa·sec, or between 500 and 5500 mPa·sec,or between 500 and 3000 mPa·sec, or between 500 and 1500 mPa·sec, and/ora viscosity of 8000 mPa·sec or less at 160° C. (as measured by ASTM D3236 at 160° C.); or 7000 or less, or 6000 or less, or 5000 or less, or4000 or less, or 3000 or less, or 1500 or less, or between 250 and 6000mPa·sec, or between 500 and 5500 mPa·sec, or between 500 and 3000mPa·sec, or between 500 and 1500 mPa·sec. In other embodiments theviscosity is 200,000 mPa·sec or less at 190° C., depending on theapplication. In other embodiments the olefin polymer may have aviscosity of about 50,000 mPa·sec or less, depending on the application.

In another embodiment the POA may also have a heat of fusion of 70 J/gor less, or 60 J/g or less, or 50 J/g or less; or 40 J/g or less, or 30J/g or less, or 20 J/g or less and greater than zero, or greater than 1J/g, or greater than 10 J/g, or between 20 and 50 J/g.

In another embodiment the oPOA may also have a Shore A Hardness (asmeasured by ASTM2240) of 95 or less, 70 or less, or 60 or less, or 50 orless, or 40 or less or 30 or less, or 20 or less. In other embodiments,the Shore A Hardness may be 5 or more, 10 or more, or 15 or more. Incertain applications, such as packaging, the Shore A Hardness ispreferably about 60-70.

In still another embodiment the POA may have a Mz/Mn of 2 to 200,preferably 2 to 150, preferably 10 to 100.

In another embodiment the POA may have a Shear Adhesion Fail Temperature(SAFT—as measured by ASTM4498) of 200° C. or less, or of 40° C. to 150°C., or 60° C. to 130° C., or 65° C. to 110° C., or 70° C. to 80° C. Incertain embodiments SAFT's of 130° C. to 140° C. may be preferred.

In another embodiment the POA may have a Dot T-Peel of between 1 Newtonand 10,000 Newtons, or 3 and 4000 Newtons, or between 5 and 3000Newtons, or between 10 and 2000 Newtons, or between 15 and 1000 Newtons.As used herein, Dot T-Peel is determined according to ASTM D 1876,except that the specimen is produced by combining two 1 inch by 3 inch(2.54 cm×7.62 cm) Kraft paper substrate cut outs with a dot of adhesivewith a volume that, when compressed under a 500 gram weight occupiesabout 1 square inch of area (1 inch=2.54 cm). Once made all thespecimens are pulled apart in side by side testing (at a rate of 2inches per minute) by a device which records the destructive force ofthe insult being applied. The maximum force achieved for each sampletested was recorded and averaged, thus producing the Average MaximumForce which is reported as the Dot T-Peel.

In another embodiment the POA may have a set time of several days toabout 0.1 seconds or less, or 60 seconds or less, or 30 seconds or less,or 20 seconds or less, or 15 seconds or less, or 10 seconds or less, or5 seconds or less, or 4 seconds or less, or 3 seconds or less, or 2seconds or less, or 1 second or less.

In another embodiment the POA may have a Mw/Mn of 2 to 75, or 4 to 60,or 5 to 50, or 6 to 20.

In yet another embodiment, the POA may have an Mz of 1,000,000 or less,preferably 15,000 to 1,000,000, or 20,000 to 800,000, or 25,000 to350,000.

In another embodiment the POA may also have a strain at break (asmeasured by ASTM D-1708 at 25° C.) of 50 to 1000%, preferably 80 to200%. In some other embodiments the strain at break is 100 to 500%.

In another embodiment, the POA has a tensile strength at break (asmeasured by ASTM D-1708 at 25° C.) of 0.5 MPa or more, alternatively0.75 MPa or more, alternatively 1.0 MPa or more, alternatively 1.5 MPaor more, alternatively 2.0 MPa or more, alternatively 2.5 MPa or more,alternatively 3.0 MPa or more, alternatively 3.5 MPa or more.

In another embodiment, the POA also has a crystallization point (Tc)between 20° C. and 110° C. In some embodiments the Tc is between 70° C.to 100° C. In other embodiments the Tc is between 30° C. and 80° C. Inother embodiments the Tc is between 20° C. and 50° C.

In some embodiments the POA may have a slope of −0.1 or less, preferably−0.15 or less, more preferably −0.25 or less in the trace of complexviscosity versus temperature as shown in FIG. 1 (as measured by ARESdynamic mechanical spectrometer operating at a frequency of 10 rad/s,with a strain of 20% under a nitrogen atmosphere, and a cooling rate of10° C./min) over the range of temperatures from Tc+10° C. to Tc+40° C.The slope is defined for use herein as a derivative of log(complexviscosity) with respect to temperature.

In another embodiment the POA has a Tc that is at least 10° C. below theTm, preferably at least 20° C. below the Tm, preferably at least 30° C.below the Tm, more preferably at least 35° C. below the Tm.

In another embodiment some POA's described above may have a melt indexratio (I₁₀/I₂) of 6.5 or less, preferably 6.0 or less, preferably 5.5 orless, preferably 5.0 or less, preferably 4.5 or less, preferably between1 and 6.0. (I₁₀ and I₂ are measured according to ASTM1238 D, 2.16 kg,190° C.).

In another embodiment some POA's described above may have a melt index(as determined by ASTM1238 D, 2.16 kg, 190° C.) of 25 dg/min or more,preferably 50 dg/min or more, preferably 100 dg/min or more, morepreferably 200 dg/min or more, more preferably 500 dg/mn or more, morepreferably 2000 dg/min or more. In another embodiment the POA has a meltindex of 900 dg/min or more.

In another embodiment the POA may have a range of crystallization of 10to 60° C. wide, preferably 20 to 50° C., preferably 30 to 45° C. in theDSC traces. In DSC traces where there are two or more non-overlappingpeaks, then each peak has a range of crystallization of 10 to 60° C.wide, preferably 20 to 50° C., preferably 30 to 45° C. in the DSCtraces.

In another embodiment the POA may have a molecular weight distribution(Mw/Mn) of at least 2, preferably at least 5, preferably at least 10,even more preferably at least 20.

In another embodiment the POA may have a unimodal, bimodal, ormultimodal molecular weight distribution (Mw/Mn) distribution of polymerspecies as determined by Size Exclusion Chromatography (SEC). By bimodalor multimodal is meant that the SEC trace has more than one peak orinflection points. An inflection point is that point where the secondderivative of the curve changes in sign (e.g., from negative to positiveor vice versus).

In another embodiment the POA may have an energy of activation of 8 to15 cal/mol. Energy of activation being calculated using therelationships of complex viscosity and temperature over the region wherethermal effects are responsible for viscosity increase (assuming anArrhenius-like relationship).

In another embodiment the POA's utilized in this invention may have acrystallinity of at least 5%.

In another embodiment the POA's described above may also have one ormore of the following:

-   -   a) a peak melting point between 60 and 190° C., or between about        60 and 150° C., or between 80 and 130° C.; and/or    -   b) a viscosity of 8000 mPa·sec or less at 190° C. (as measured        by ASTM D 3236 at 190° C.); or 5000 or less, or 4000 or less, or        3000 or less, or 1500 or less, or between 250 and 6000 mPa·sec,        or between 500 and 5500 mPa·sec, or between 500 and 3000        mPa·sec, or between 500 and 1500 mPa·sec, or a viscosity of 8000        mPa·sec or less at 160° C. (as measured by ASTM D 3236 at 160°        C.); or 7000 or less, or 6000 or less, or 5000 or less, or 4000        or less, or 3000 or less, or 1500 or less, or between 250 and        6000 mPa·sec, or between 500 and 5500 mPa·sec, or between 500        and 3000 mPa·sec, or between 500 and 1500 mPa·sec; and/or    -   c) an H_(f) (Heat of fusion) of 70 J/g or less, or 60 J/g or        less, or 50 J/g or less; or 40 J/g or less, or 30 J/g or less,        or 20 J/g or less and greater than zero, or greater than 1 J/g,        or greater than 10 J/g, or between 20 and 50 J/g; and or    -   d) a Shore A Hardness (as measured by ASTM2240) of 90 or less,        or 80 or less, or 70 or less, or 60 or less or 50 or less, or 40        or less; and or    -   e) a Shear Adhesion Fail Temperature (SAFT—as measured by        ASTM4498) of 40 to 150° C., or 60 to 130° C., or 65 to 110° C.,        or 70-80° C.; and or;    -   f) a Dot T-Peel of between 1 Newton and 10,000 Newtons, or 3 and        4000 Newtons, or between 5 and 3000 Newtons, or between 10 and        2000 Newtons, or between 15 and 1000 Newtons; and/or    -   g) a set time of several days to 0.1 second, or 60 seconds or        less, or 30 seconds or less, or 20 seconds or less, or 15        seconds or less, or 10 seconds or less, or 5 seconds or less, or        4 seconds or less, or 3 seconds or less, more or 2 seconds or        less, or 1 second or less; and or    -   h) an Mw/Mn of greater than 1 to 75, or 2 to 60, or 2 to 50, or        3 to 20; and/or    -   i) an Mz of 1,000,000 or less, preferably 15,000 to 500,000, or        20,000 to 400,000, or 25,000 to 350,000.

Useful combinations of features include POA's having a Dot T-Peel ofbetween 1 Newton and 10,000 Newtons, or 3 and 4000 Newtons, or between 5and 3000 Newtons, or between 10 and 2000 Newtons, or between 15 and 1000Newtons and:

1. an Mw of 30,000 or less, a peak melting point between 60 and 190° C.,a Heat of fusion of 1 to 70 J/g, a branching index (g′) of 0.90 or lessmeasured at the Mz of the polymer; and a melt viscosity of 8000 mPa·secor less at 190° C.; or

2. an Mz of 20,000 to 500,000 and a SAFT of 60 to 150° C.; or

3. an Mz/Mn of 2-200 and a set time of 2 seconds or less; or

4. an H_(f) (heat of fusion) of 20 to 50 J/g, an Mz or 20,000-500,000and a shore hardness of 50 or less; or

5. an Mw/Mn of greater than 1 to 50, a viscosity of 5000 or less mPa·secat 190° C.; or

6. an Mw of 50,000 or less, a peak melting point between 60 and 190° C.,a heat of fusion of 2 to 70 J/g, a branching index (g′) of 0.70 or lessmeasured at the Mz of the polymer, and a melt viscosity of 8000 mPa·secor less at 190° C.

In a preferred embodiment, the POA comprises amorphous, crystalline andbranch-block molecular structures.

In a preferred embodiment the POA comprises at least 50 weight %propylene, preferably at least 60% propylene, alternatively at least 70%propylene, alternatively at least 80% propylene. In another embodimentthe POA comprises propylene and 15 mole % ethylene or less, preferably10 mole % ethylene or less, more preferably 9 mole % ethylene or less,more preferably 8 mole % ethylene or less, more preferably 7 mole %ethylene or less, more preferably 6 mole % ethylene or less, morepreferably 5 mole % ethylene or less, more preferably 4 mole % ethyleneor less, more preferably 3 mole % ethylene or less, more preferably 2mole % ethylene or less, more preferably 1 mole % ethylene or less.

In another embodiment the POA comprises less than 5 mole % of ethylene,preferably less than 4.5 mole % ethylene, preferably less than 4.0 mole% ethylene, alternatively less than 3.5 mole % ethylene, alternativelyless than 3.0 mole % ethylene, alternatively less than 2.5 mole %ethylene, alternatively less than 2.0 mole % ethylene, alternativelyless than 1.5 mole % ethylene, alternatively less than 1.0 mole %ethylene, alternatively less than 0.5 mole % ethylene, alternativelyless than 0.25 mole % ethylene, alternatively 0 mole % ethylene.

In another embodiment the POA has a glass transition temperature (Tg) asmeasured by ASTM E 1356 of 5° C. or less, preferably 0° C. or less,preferably −5° C. or less, alternatively between −5° C. and −40° C.,alternatively between −5° C. and −15° C.

In another embodiment the POA has an amorphous content of at least 50%,alternatively at least 60%, alternatively at least 70%, evenalternatively between 50 and 99%. Percent amorphous content isdetermined using Differential Scanning calorimetry measurement accordingto ASTM E 794-85.

In another embodiment the POA has a crystallinity of 40% or less,alternatively 30% or less, alternatively 20% or less, even alternativelybetween 10% and 30%. Percent crystallinity content is determined usingDifferential Scanning calorimetry measurement according to ASTM E794-85. In another embodiment, the POA's described herein have a percentcrystallinity of between 5 and 40%, alternatively between 10 to 30%.

In another embodiment the POA may have a molecular weight distribution(Mw/Mn) of at least 1.5, preferably at least 2, preferably at least 5,preferably at least 10, even alternatively at least 20. In otherembodiments the Mw/Mn is 20 or less, 10 or less, even 5 or less.Molecular weight distribution generally depends on the catalysts usedand process conditions such as temperature, monomer concentration,catalyst ratio, if multiple catalysts are used, and the presence orabsence of hydrogen. Hydrogen may be used at amounts up to 2 weight %,but is preferably used at levels of 50 to 500 ppm.

In another embodiment the POA may be found to have at least twomolecular weights fractions present at greater than 2 weight %,preferably greater than 20 weight %, each based upon the weight of thepolymer as measured by Gel Permeation Chromatography. The fractions canbe identified on the GPC trace by observing two distinct populations ofmolecular weights. An example would be a GPC trace showing a peak at20,000 Mw and another peak at 50,000 Mw where the area under the firstpeak represents more than 2 weight % of the polymer and the area underthe second peak represents more than 2 weight % of the polymer.

In another embodiment the POA of this invention may have 20 weight % ormore (based upon the weight of the starting polymer) of hexane roomtemperature soluble fraction, and 70 weight % or less, preferably 50weight % or less of Soxhlet boiling heptane insolubles, based upon theweight of the polymer. Soxhlet heptane insoluble refers to one of thefractions obtained when a sample is fractionated using successivesolvent extraction technique. The fractionations are carried out in twosteps: one involves room temperature solvent extraction, the othersoxhlet extraction. In the room temperature solvent extraction, aboutone gram of polymer is dissolved in 50 ml of solvent (e.g., hexane) toisolate the amorphous or very low molecular weight polymer species. Themixture is stirred at room temperature for about 12 hours. The solublefraction is separated from the insoluble material using filtration undervacuum. The insoluble material is then subjected to a Soxhlet extractionprocedure. This involves the separation of polymer fractions based ontheir solubility in various solvents having boiling points from justabove room temperature to 110° C. The insoluble material from the roomtemperature solvent extraction is first extracted overnight with asolvent such as hexane and heptane (Soxhlet); the extracted material isrecovered by evaporating the solvent and weighing the residue. Theinsoluble sample is then extracted with a solvent having higher boilingtemperature such as heptane and after solvent evaporation, it isweighed. The insolubles and the thimble from the final stage areair-dried in a hood to evaporate most of the solvent, then dried in anitrogen-purged vacuum oven. The amount of insoluble left in the thimbleis then calculated, provided the tare weight of the thimble is known.

In another embodiment, the POA's may have a heptane insoluble fraction70 weight % or less, based upon the weight of the starting polymer, andthe heptane insoluble fraction has branching index g′ of 0.9 (preferably0.7) or less as measured at the Mz of the polymer. In a preferredembodiment the composition may also have at least 20 weight % hexanesoluble fraction, based upon the weight of the starting polymer. Inanother embodiment, the POA's may have a heptane insoluble fraction 70weight % or less, based upon the weight of the starting polymer and a Mzbetween 20,000 and 5000,000 of the heptane insoluble portion. In apreferred embodiment the composition also has at least 20 weight %hexane soluble fraction, based upon the weight of the starting polymer.In another embodiment the POA's have a hexane soluble portion of atleast 20 weight %, based upon the weight of the starting polymer.

In another embodiment the POA comprises propylene and 15 mole % ethyleneor less, preferably 10 mole % ethylene or less, more preferably 9 mole %ethylene or less, more preferably 8 mole % ethylene or less, morepreferably 7 mole % ethylene or less, more preferably 6 mole % ethyleneor less, more preferably 5 mole % ethylene or less, more preferably 4mole % ethylene or less, more preferably 3 mole % ethylene or less, morepreferably 2 mole % ethylene or less, more preferably 1 mole % ethyleneor less.

In another embodiment the POA comprises less than 5 mole % of ethylene,preferably less than 4.5 mole % ethylene, preferably less than 4.0 mole% ethylene, alternatively less than 3.5 mole % ethylene, alternativelyless than 3.0 mole % ethylene, alternatively less than 2.5 mole %ethylene, alternatively less than 2.0 mole % ethylene, alternativelyless than 1.5 mole % ethylene, alternatively less than 1.0 mole %ethylene, alternatively less than 0.5 mole % ethylene, alternativelyless than 0.25 mole % ethylene, alternatively 0 mole % ethylene.

For ease of reference the portion of the olefin polymer produced by oneof the catalyst may have at least 10% crystallinity may also be referredto as the “semi-crystalline polymer” and the polymer produced by anotherof the catalyst may have a crystallinity of less than 5%, which may bereferred to as the “amorphous polymer.”

In another embodiment of this invention the POA may have acharacteristic three-zone complex viscosity-temperature pattern,consistent with that shown in FIG. 1. The temperature dependence ofcomplex viscosity was measured using ARES dynamic mechanicalspectrometer operating at a frequency of 10 rad/s, with a strain of 20%under a nitrogen atmosphere, and a cooling rate of 10° C./min. Thesample was first molten then gradually cooled down to room temperaturewhile monitoring the build-up in complex viscosity. Above the meltingpoint, which is typical of polymer processing temperature, the complexviscosity is relatively low (Zone I) and increases gradually withdecreasing temperature. In zone II, a sharp increase in complexviscosity appears as temperature is dropped. The third zone (Zone III)is the high complex viscosity zone, which appears at lower temperaturescorresponding to application (end use) temperatures. In Zone III thecomplex viscosity is high and varies slightly with further decrease intemperature. Such a complex viscosity profile provides, in hot meltadhesive applications, a desirable combination of long opening time atprocessing temperatures and fast set time at lower temperatures.

In a preferred embodiment, the POA's have less than 1 mol % ethylene,have at least 2 mol % (CH₂)₂ units, preferably 4 mol %, preferably 6 mol%, more preferably 8 mol %, more preferably 10 mol %, more preferably 12mol %, more preferably 15 mol %, more preferably 18 mol %, morepreferably 5 mol % as measured by Carbon 13 NMR as described below.

In an another embodiment, the POA's may have between 1 and 10 mol %ethylene, have at least 2+X mol % (CH₂)₂ units, preferably 4+X mol %,preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+Xmol %, more preferably 12+X mol %, more preferably 15+X mol %, morepreferably 18+X mol %, more preferably 20+X mol %, where X is the mole %of ethylene, and the (CH₂)₂ units are determined by Carbon 13 NMR asdescribed below.

In a preferred embodiment, the POA's may have less than 1 mol %ethylene, have an amorphous component (i.e., defined to be that portionof the polymer composition that has a crystallinity of less than 5%)which contains at least 3 mol % (CH₂)₂ units, preferably 4 mol %,preferably 6 mol %, more preferably 8 mol %, more preferably 10 mol %,more preferably 12 mol %, more preferably 15 mol %, more preferably 18mol %, more preferably 20 mol % as measured by Carbon 13 NMR asdescribed below.

In an another embodiment, the POA's may have between 1 and 10 mol %ethylene, have an amorphous component (which is defined to be thatportion of the polymer composition that has a crystallinity of less than5%) which contains at least 3+X mol % (CH₂)₂ units, preferably 4+X mol%, preferably 6+X mol %, more preferably 8+X mol %, more preferably 10+Xmol %, more preferably 12+X mol %, more preferably 15+X mol %, morepreferably 18+X mol %, more preferably 20+X mol %, where X is the mole %of ethylene, and the (CH₂)₂ units are determined by Carbon 13 NMR asdescribed below.

Functionalized C3-C40 Olefin Polymers (F-POA's)

Any of the polymers described above as POA's may be functionalized andused as F—POA's. Typically, the POA is combined with a free radicalinitiator and a grafting monomer or other functional group (such asmaleic acid or maleic anhydride) and is heated to react the monomer withthe POA to form the F-POA.

As stated above, the present invention comprises a functionalized olefinpolymer or blend of functionalized olefin polymers, also referred toherein as grafted olefin polymers. By functionalized (or grafted) it ismeant that various functional groups are incorporated, grafted, bondedto, and/or physically or chemically attached to the polymer backbone ofthe POA being functionalized.

In one embodiment, functional groups are grafted onto the POA utilizingradical copolymerization of an functional group, referred to herein asgraft copolymerization.

Examples of suitable functional groups include unsaturated carboxylicacids, esters of the unsaturated carboxylic acids, acid anhydrides,di-esters, salts, amides, imides, aromatic vinyl compounds hydrolyzableunsaturated silane compounds and unsaturated halogenated hydrocarbons.Preferred examples of unsaturated carboxylic acids and acid derivativesinclude, but are not limited to maleic anhydride, citraconic anhydride,2-methyl maleic anhydride, 2-chloromaleic anhydride, 2,3-dimethylmaleicanhydride, bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride and4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid,methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconicacid, mesaconic acid, crotonic acid,bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride, 1,2,3,4,5,&g,lo-octahydronaphthalene-2,3-dicarboxylic acid anhydride,2-oxa-1,3-diketospiro(4.4)non-7-ene,bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride, maleopimaricacid, tetrahydrophtalic anhydride, norborn-5-ene-2,3-dicarboxylic acidanhydride, nadic anhydride, methyl nadic anhydride, himic anhydride,methyl himic anhydride, andx-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride(XMNA).

Examples of the esters of the unsaturated carboxylic acids includemethyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate,ethyl methacrylate and butyl methacrylate.

Hydrolyzable unsaturated silane compounds useful as functional groupsherein may include radical polymerizable unsaturated group and analkoxysilyl group or a silyl group in its molecule, such that thecompound has a hydrolyzable silyl group bonded to a vinyl group and/or ahydrolyzable silyl group bonded to the vinyl group via an alkylenegroup, and/or a compound having a hydrolyzable silyl group bonded to anester or an amide of acrylic acid, methacrylic acid or the like.Examples thereof include vinyltrichlorosilane,vinyltris(beta-methoxyethoxy)silane, vinyltriethoxysilane,vinyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilanemonovinylsilane and monoallylsilane.

Examples of unsaturated halogenated hydrocarbons useful as functionalgroups herein include vinyl chloride and vinylidene chloride.

In a preferred embodiment, the POA is grafted with maleic anhydride(MA), to produce olefin grafted maleic anhydride (POA-g-MA), wherein themaleic anhydride is bonded to the polymer chain of the polymericcomposition.

Preferable examples of the radical initiator used in the graftcopolymerization include organic peroxides such as benzoyl peroxide,methyl ethyl ketone peroxide, cyclohexanone peroxide,t-butylperoxyisopropyl carbonate, di-ti-butyl perphthalate,2,5-dimethyl-2,5-di(t-butylperoxy)hexene,2,5-dimethyl-2,5-di(t-butylperoxy)hexene-3, di-t-butyl peroxide, cumenehydroperoxide, t-butyl hydroperoxide, dilauryl peroxide and dicumylperoxide.

The F-POA of the present invention may thus be obtained by heating thePOA(s) and the functional group(s) in the presence of the radicalinitiator at, near, or above a decomposition temperature of the radicalinitiator.

In some embodiments, no particular restriction need be put on the amountof the functional group to be used, accordingly, conventional conditionsfor functionalizing, for example, an isotactic polypropylene, can beutilized with the POA's of this invention. Since in some cases theefficiency of the copolymerization is relatively high, the amount of thefunctional group may be small. In an embodiment, the amount of thefunctional group to be incorporated into the POA is preferably fromabout 0.001 to 50 wt % functional group with respect to the total amountof olefin polymer present, preferably from 0.005 to 40 weight %,preferably from 0.01 to 35 weight %, preferably from about 0.05 to about30 weight %, more preferably from about 0.1 to about 25 weight %,preferably from about 0.5 to about 20 weight %, preferably from about1.0 to about 15 weight %, preferably from about 1.5 to 10 weight %,preferably from about 2 to 5 weight %, preferably from about 2 to about4 weight %. In a preferred embodiment, the amount of the maleic acidand/or maleic anhydride, preferably maleic anhydride, to be incorporatedinto the POA is preferably from about 0.001 to about 50 wt %, based uponthe weight of the POA, preferably from 0.005 to 40 weight %, preferablyfrom 0.01 to 35 weight %, preferably from about 0.05 to about 30 weight%, more preferably from about 0.1 to about 25 weight %, preferably fromabout 0.5 to about 20 weight %, preferably from about 1.0 to about 15weight %, preferably from about 1.5 to 10 weight %, preferably fromabout 2 to 5 weight %, preferably from about 2 to about 4 weight %.

The radical initiator is preferably used in a ratio of from 0.00001 to10 wt %, based on the weight of the functional group. The heatingtemperature depends upon whether or not the reaction is carried out inthe presence of a solvent, but it is usually from about 50° C. to 350°C. When the heating temperature is less than 50° C., the reaction may beslow and thus efficiency may be low. When it is more than 350° C.,decomposition of the POA may occur.

The F-POA may be functionalized with an functional group utilizing asolvent based functionalization process and/or utilizing a melt basedfunctionalization process without a solvent. In the solvent basedprocess, the reaction may be carried out using the POA in the form of asolution or a slurry having a concentration of from 0.1 to 50 wt % inthe presence of a halogenated hydrocarbon compound having 2 to 20 carbonatoms, an aromatic compound, a halogenated aromatic compound, an alkylsubstituted aromatic hydrocarbon, a cyclic hydrocarbon, and/or ahydrocarbon compound having 6 to 20 carbon atoms which is stable to theradicals.

The POA may also be functionalized in a process utilizing a melt basedfunctionalization process without a solvent. Such a reaction may becarried out in the absence of the solvent in a device such as anextruder which can sufficiently produce physical contact between thePOA, and the unsaturated monomer. In the latter case, the reaction isusually effected at a relatively high temperature, as compared with thereaction in the state of the solution.

Other methods for functionalizing POA's that may be used include, butare not limited to, selective oxidation, ozonolysis, epoxidation, andthe like, both in solution or slurry (i.e., with a solvent), or in amelt (i.e., without a solvent) as described above.

In the present invention, the graft polymerization (grafting of the POA)may also be carried out in an aqueous medium. In this case a dispersantcan be used, and examples of the dispersant include a saponifiedpolyvinyl acetate, modified celluloses such as hydroxyethyl celluloseand hydroxypropyl cellulose, and compounds containing an OH group suchas polyacrylic acid and polymethacrylic acid. In addition, compoundswhich are used in a usual aqueous suspension polymerization can also bewidely employed.

The reaction may be carried out by suspending the POA, thewater-insoluble radical polymerizable monomer, the water-insolubleradical initiator and/or the dispersant in water, and then heating themixture. Here, a ratio of water to the sum of the radical polymerizablemonomer (i.e., the functional group) and the POA is preferably 1:0.1 to1:200, more preferably 1:1 to 1:100. The heating temperature is suchthat the half-life of the radical initiator is preferably from 0.1 to100 hours, more preferably from 0.2 to 10 hours, and it is preferablyfrom 30° to 200° C., more preferably from 40° to 150° C. In the heatingstep, it is preferred that the mixture is stirred sufficiently so as tobecome in a suspension state. In this way, the F-PAO may be obtained ingranular form.

A weight ratio of the water-insoluble monomer to the POA may preferablybe from 1:01 to 1:10000, and a weight ratio of the radical initiator tothe water-insoluble monomer may be from 0.00001 to 0.1. The ratio of thewater-insoluble monomer in theF-POA depends upon its use, but the amountof the monomer may be from 0.1 to 200% by weight based on the weight ofthe POA present in the F-POA.

The F-POA preferably contains a desired amount of radical polymerizablefunctional group units in the range of from 0.1 to 50 wt % based on theweight of the POA in compliance with its intended use or application.

Furthermore, a compatibilizing effect within the inventive compositionobtained by inclusion of the F-POA may be influenced by the level ofgrafting. In an embodiment, the POA may be functionalized to includeabout 0.001 wt % or greater of the functional group attached. The POAmay also be functionalized grafted to a higher degree. The level offunctionalization (e.g., the grafting level) may be less than about 50wt %, preferably less than about 45 wt %, preferably less than about 40wt %, preferably less than about 35 wt %, preferably less than about 30wt %, preferably less than about 25 wt %, preferably less than about 20wt %, preferably less than about 15 wt %, preferably less than about 10wt %, preferably less than about 9 wt %, preferably less than about 8 wt%, preferably less than about 7 wt %, preferably less than about 6 wt %,preferably less than about 5 wt %, preferably less than about 4 wt %,preferably less than about 3 wt %, preferably less than about 2 wt %,preferably less than about 1.5 wt %, preferably less than about 1 wt %,preferably less than about 0.5 wt %.

The F-PAO may be a single POA which has been functionalized as describedherein. In another embodiment, the F-POA of the present invention may bea blend of POA's which are functionalized together during a singleprocess. The F-POA's of the present invention may also include aplurality of F-POA's which are combined after being individuallyfunctionalized, or any combination thereof.

In another aspect this invention provides the ability to produceadhesives that may be do not have to be further blended or modified.

Accordingly, this invention also further relates to a continuous processto prepare an F-PAO comprising the steps of:

1) combining monomer, optional solvent, catalyst and activator in areactor system;

2) withdrawing PAO solution from the reactor system;

3) removing at least 10% solvent, if present, from the PAO solution;

4) quenching the reaction;

5) devolatilizing the PAO solution to form molten PAO;

6) combining at least a portion of the molten PAO with an functionalgroup (preferably maleic anhydride) in the presence of a radicalinitiator at a temperature, and for a period of time sufficient toproduce F-PAO;

7) combining F-PAO, optionally PAO, and optionally one or more additives(such as those described below) in a mixer, such as a static mixer, (ina preferred embodiment tackifer is not added or is added in amounts ofless than 30 weight %, preferably less than 20 weight %, more preferablyin amounts of less than 10 weight %), and mixing to produce theinventive compositon;

8) removing the composition from the mixer, and

9) pelletizing or drumming the composition;

where step 1) comprises any of the processes described herein for theproduction of PAO.

In another embodiment this invention relates to a continuous process toprepare an adhesive comprising:

1) combining monomer, optional solvent, catalyst and activator in areactor system;

2) withdrawing PAO solution from the reactor system;

3) removing at least 10% solvent, if present, from the PAOsolution;

4) quenching the reaction;

5) devolatilizing the PAO solution to form molten PAO;

6) combining at least a portion of the molten PAO with an functionalgroup in the presence of a radical initiator for a period of timesufficient to graft the functional group into the PAO to produce F-PAO;

7) combining the molten F-PAO, the PAO, and one or more additives in amixer, such as a static mixer;

8) removing the polymer combination from the mixer; and

9) pelletizing or drumming the polymer combination.

In a particularly preferred embodiment, this invention relates to acontinuous process to make an adhesive comprising:

1) selecting a first catalyst component capable of producing a polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or less(preferably 5% or less) under selected polymerization conditions;

2) selecting a second catalyst component capable of producing polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or more(preferably 40% or more) at the selected polymerization conditions;

3) contacting, in a solvent and in a reaction zone under the selectedpolymerization conditions, the catalyst components in the presence ofone or more activators with one or more C3 to C40 olefins, and,optionally one or more diolefins;

4) at a temperature of greater than 70° C., preferably greater than 100°C.;

5) at a residence time of up to 120 minutes, (preferably 60 minutes orless);

6) wherein the ratio of the first catalyst to the second catalyst isfrom 1:1 to 50:1; 7) wherein the activity of the catalyst components isat least 50 kilograms of polymer per gram of the catalyst components;and wherein at least 20% of the olefins are converted to polymer;

8) withdrawing olefin polymer solution from the reaction zone;

9) removing at least 10% solvent from the olefin polymer solution;

10) quenching the reaction;

11) devolatilizing the olefin polymer solution to form molten olefinpolymer;

12) combining at least a portion of the molten olefin polymer with anfunctional group in the presence of a radical initiator at atemperature, and for a period of time sufficient to produce thefunctionalized olefin polymer (e.g., to graft the functional group intothe olefin polymer);

13) combining the molten functionalized olefin polymer, the olefinpolymer, and one or more additives in a mixer, such as a static mixer toproduce the inventive composition;

14) removing the olefin polymer combination (the composition) from themixer; and

15) pelletizing or drumming the composition.

In a particularly preferred embodiment, this invention relates to acontinuous process to make an adhesive comprising:

1) selecting a first catalyst component capable of producing a polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or less(preferably 5% or less) under selected polymerization conditions;

2) selecting a second catalyst component capable of producing polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or more(preferably 40% or more) at the selected polymerization conditions;

3) contacting, in a solvent and in a reaction zone under the selectedpolymerization conditions, the catalyst components in the presence ofone or more activators with one or more C3 to C40 olefins, and,optionally one or more diolefins;

4) at a temperature of greater than 70° C., preferably greater than 100°C.;

5) at a residence time of 120 minutes or less, preferably 60 minutes orless;

6) wherein the ratio of the first catalyst to the second catalyst isfrom 1:1 to 50:1, preferably 1:1 to 30:1;

7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst components; and wherein atleast 50% of the olefins are converted to polymer;

8) withdrawing olefin polymer solution from the reaction zone;

9) removing at least 10% solvent from the olefin polymer solution;

10) quenching the reaction;

11) forming molten olefin polymer where the polymer comprises one ormore C3 to C40 olefins, and less than 5 mole % of ethylene, and wherethe polymer has:

-   -   a) a Dot T-Peel of 1 Newton or more;    -   b) a branching index (g′) of 0.95 or less measured at the Mz of        the polymer; and    -   c) a Mw of 100,000 or less;

12) combining at least a portion of the molten olefin polymer with anfunctional group in the presence of a radical initiator at a temperatureand for a period of time sufficient to produce the functionalized olefinpolymer;

13) combining the molten functionalized olefin polymer, the olefinpolymer, and one or more additives in a mixer, such as a static mixerand mixing to produce a composition;

14) removing the composition from the mixer; and

15) pelletizing or drumming the composition.

In a particularly preferred embodiment, this invention relates to acontinuous process to make an adhesive comprising

1) selecting a first catalyst component capable of producing a polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or less,(preferably 5% or less) under selected polymerization conditions;

2) selecting a second catalyst component capable of producing polymerhaving an Mw of 100,000 or less and a crystallinity of 20% or more(preferably 40% or more) at the selected polymerization conditions;

3) contacting, in a solvent and in a reaction zone under the selectedpolymerization conditions, the catalyst components in the presence ofone or more activators with one or more C3 to C40 olefins, and,optionally one or more diolefins;

4) at a temperature of greater than 70° C., preferably greater than 100°C.;

5) at a residence time of 120 minutes or less, preferably 60 minutes ofless;

6) wherein the ratio of the first catalyst to the second catalyst isfrom 1:1 to 50:1, preferably from 1:1 to 30:1;

7) wherein the activity of the catalyst components is at least 50kilograms of polymer per gram of the catalyst components; and wherein atleast 50% of the olefins are converted to polymer;

8) withdrawing olefin polymer solution from the reaction zone;

9) removing at least 10% solvent from the olefin polymer solution;

10) quenching the reaction;

11) forming molten olefin polymer where the olefin polymer comprises atleast 50 mole % of one or more C3 to C40 olefins (preferably propylene),and less than 5 mole % of ethylene, and where the polymer has:

-   -   a) a Dot T-Peel of 3 Newton or more; and    -   b) a branching index (g′) of 0.90 or less measured at the Mz of        the polymer; and    -   c) an Mw of 30,000 or less;    -   d) a peak melting point between 60 and 190° C.,    -   e) a Heat of fusion of 1 to 70 J/g,    -   f) a melt viscosity of 8000 mPa·sec or less at 190° C.;

12) combining at least a portion of the molten olefin polymer with anfunctional group in the presence of a radical initiator for a period oftime sufficient to produce the functionalized olefin polymer;

13) combining the molten functionalized olefin polymer, the olefinpolymer, and one or more additives in a mixer, such as a static mixerand mixing to produce the inventive composition;

14) removing the inventive olefin polymer combination from the mixer;and

15) pelletizing or drumming the inventive olefin polymer combination.

Blending of Functionalized Olefin Polymers

The F-PAO may be mixed or blended with (i.e., in combination with, anadmixture of, and the like) one or more other polymer. Preferredpolymers include olefin homopolymers or copolymer containing no graftcomponent, a different graft component, or a similar graft component ata different level of inclusion, and/or the like, to achieve a finalcomposition with a desired level of adhesion for a particular end use orprocess.

In an embodiment, the olefin homopolymer or copolymer to be bleded withthe F-POA may also be an alpha-olefin homopolymer or copolymercontaining no graft component. If desired, the alpha-olefin homopolymersmay have various molecular weight characteristics, may be random and/orblock copolymers of alpha-olefins themselves. Examples of thealpha-olefin include ethylene and alpha-olefins having 4 to 20 carbonatoms in addition to propylene. The homopolymers and copolymers of thesealpha-olefins can be manufactured by various known methods, and may becommercially available under various trade names.

In a preferred embodiment the F-POA is combined with one or more otherpolymers, including but not limited to, thermoplastic polymer(s) and/orelastomer(s).

By thermoplastic polymer(s)” is meant a polymer that can be melted byheat and then cooled with out appreciable change in properties.Thermoplastic polymers typically include, but are not limited to,polyolefins, polyamides, polyesters, polycarbonates, polysulfones,polyacetals, polylactones, acrylonitrile-butadiene-styrene resins,polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrileresins, styrene maleic anhydride, polyimides, aromatic polyketones, ormixtures of two or more of the above. Preferred polyolefins include, butare not limited to, polymers comprising one or more linear, branched orcyclic C2 to C40 olefins, preferably polymers comprising propylenecopolymerized with one or more C3 to C40 olefins, preferably a C3 to C20alpha olefin, more preferably C3 to C10 alpha-olefins. More preferredpolyolefins include, but are not limited to, polymers comprisingethylene including but not limited to ethylene copolymerized with a C3to C40 olefin, preferably a C3 to C20 alpha olefin, more preferablypropylene and or butene.

By elastomers is meant all natural and synthetic rubbers, includingthose defined in ASTM D1566). Examples of preferred elastomers include,but are not limited to, ethylene propylene rubber, ethylene propylenediene monomer rubber, styrenic block copolymer rubbers (including SI,SIS, SB, SBS, SIBS and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).

In another embodiment, the F-POA is combined with one or more ofisotactic polypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, random copolymer of propylene and ethylene and/or buteneand/or hexene, polybutene, ethylene vinyl acetate, low densitypolyethylene (density 0.915 to less than 0.935 g/cm³) linear low densitypolyethylene, ultra low density polyethylene (density 0.86 to less than0.90 g/cm³), very low density polyethylene (density 0.90 to less than0.915 g/cm³), medium density polyethylene (density 0.935 to less than0.945 g/cm³), high density polyethylene (density 0.945 to 0.98 g/cm³),ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylicacid, polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR),vulcanized EPR, EPDM, block copolymer, styrenic block copolymers,polyamides, polycarbonates, PET resins, crosslinked polyethylene,copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromaticmonomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidinefluoride, polyethylene glycols and/or polyisobutylene.

In a preferred embodiment the F-POA is combined with metallocenepolyethylenes (mPE's) or metallocene polypropylenes (mPP's). The mPE andmPP homopolymers or copolymers are typically produced using mono- orbis-cyclopentadienyl transition metal catalysts in combination with anactivator of alumoxane and/or a non-coordinating anion in solution,slurry, high pressure or gas phase. The catalyst and activator may besupported or unsupported and the cyclopentadienyl rings by maysubstituted or unsubstituted. Several commercial products produced withsuch catalyst/activator combinations are commercially available fromExxon Chemical Company in Baytown, Tex. under the tradenames EXCEED™,ACHIEVE™ and EXACT™. For more information on the methods andcatalysts/activators to produce such homopolymers and copolymers see WO94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Pat. No.5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat.No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129,368; U.S.Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat. No. 5,096,867;U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495375; EPA 500 944; EPA 570 982; WO91/09882; WO94/03506 and U.S. Pat. No.5,055,438.

In a preferred embodiment the F-POA is present in the in the aboveblends, at from 10 to 99 weight %, based upon the weight of the polymersin the blend, preferably 20 to 95 weight %, even more preferably atleast 30 to 90 weight %, even more preferably at least 40 to 90 weight%, even more preferably at least 50 to 90 weight %, even more preferablyat least 60 to 90 weight %, even more preferably at least 70 to 90weight %.

In the process utilized for producing the F-POA no particularrestriction need be put on a mixing manner, accordingly, the rawmaterials may be mixed uniformly by means of a Henschel mixer or thelike and then may be melted, mixed and molded into pellets by anextruder or the like. The blends described herein may be formed usingconventional techniques known in the art such that blending may beaccomplished using one or more static mixers, in-line mixers, elbows,orifices, baffles, or any combination thereof. It is also possible toutilize a Brabender mixer by which mixing and melting are carried outsimultaneously, and after the melting, the material can be directlymolded into films, sheets, or the like.

In a preferred embodiment, the weight to weight ratio of POA to F-POA(preferably POA-g-MA), is in the range of about 1:1000 to 1000:1. Inanother preferred embodiment the weight to weight ratio of F-POA(preferably POA-g-MA) to POA, is preferably 1:100 or less, about 1:50 orless, about 1:20 or less, about 1:10 or less, about 1:5 or less, about1:4 or less, about 1:3 or less, about 1:2 or less, or about 1:1. Inanother embodiment the weight to weight ratio of the F-POA to the POAmay be about 100:1, about 50:1, about 20:1, about 10:1, about 5:1, about4:1, about 3:1, or about 2:1.

The composition comprising the F-POA, blends of F-POA's and/or anadmixture of POA and F-POA, as produced herein, may be used directly asan adhesive, or may be blended, mixed and/or combined with othercomponents to form an adhesive formulation.

Tackifiers may be used with the compositions of the present invention.Examples of suitable tackifiers, include, but are not limited to,aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbonresins, hydrogenated polycyclopentadiene resins, polycyclopentadieneresins, gum rosins, gum rosin esters, wood rosins, wood rosin esters,tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modifiedpolyterpenes, terpene phenolics, aromatic modified hydrogenatedpolycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenatedaliphatic aromatic resins, hydrogenated terpenes and modified terpenes,hydrogenated rosin acids, and hydrogenated rosin esters. In someembodiments the tackifier may be hydrogenated.

In other embodiments, the tackifier may be non-polar. (Non-polar meaningthat the tackifier is substantially free of monomers having polargroups. Preferably, the polar groups are not present, however if theyare present, they are preferably not present at more that 5 weight %,preferably not more that 2 weight %, even more preferably no more than0.5 weight %.) In some embodiments the tackifier may have a softeningpoint (Ring and Ball, as measured by ASTM E-28) of 80° C. to 150° C.,preferably 100° C. to 130° C. In another embodiment the resins is liquidand has a R and B softening point of between 10 and 70° C.

The tackifier, if present in the composition, may comprise about 0.1 toabout 80 wt %, based upon the weight of the composition, more preferably2 to 40 weight %, even more preferably 3 to 30 weight %.

Preferred hydrocarbon resins for use as tackifiers or modifiers include:

-   -   1. Resins such as C₅/C₆ terpene resins, styrene terpenes,        alpha-methyl styrene terpene resins, C₉ terpene resins, aromatic        modified C₅/C₆, aromatic modified cyclic resins, aromatic        modified dicyclopentadiene based resins or mixtures thereof.        Additional preferred resins include those described in WO        91/07472, U.S. Pat. No. 5,571,867, U.S. Pat. No. 5,171,793 and        U.S. Pat. No. 4,078,132. Typically these resins are obtained        from the cationic polymerization of compositions containing one        or more of the following monomers: C₅ diolefins (such as 1-3        pentadiene, isoprene, and the like); C₅ olefins (such as        2-methylbutenes, cyclopentene, and the like); C₆ olefins (such        as hexene), C₉ vinylaromatics (such as styrene, alpha methyl        styrene, vinyltoluene, indene, methyl indene, and the like);        cyclics (such as dicyclopentadiene, methyldicyclopentadiene, and        the like); and or terpenes (such as limonene, carene, thujone,        and the like).    -   2. Resins obtained by the thermal polymerization of        dicyclopentadiene, and/or the thermal polymerization of dimers        or oligomers of cyclopentadiene and/or methylcyclopentadiene,        optionally with vinylaromatics (such as styrene, alpha-methyl        styrene, vinyl toluene, indene, methyl indene, and the like).

The resins obtained after polymerization and separation of unreactedmaterials, can be hydrogenated if desired. Examples of preferred resinsinclude those described in U.S. Pat. No. 4,078,132; WO 91/07472; U.S.Pat. No. 4,994,516; EP 0 046 344 A; EP 0 082 726 A; and U.S. Pat. No.5,171,793.

Crosslinking Agents

In another embodiment the composition of this invention may furthercomprises a crosslinking agent. Preferred crosslinking agents includethose having functional groups that can react with the acid or anhydridegroup. Preferred crosslinking agents include alcohols, multiols, amines,diamines and/or triamines Particular examples of crosslinking agentsuseful in this invention include polyamines such as ethylenediamine,diethylenetriamine, hexamethylenediamine, diethylaminopropylamine,and/or menthanediamine.

Of the F-POA's of the present invention, a copolymer in which anhydrolyzable unsaturated silane is grafted can be utilized as a startingmaterial for a crosslinked polypropylene or a crosslinked propylenecopolymer. In this case, the hydrolyzable unsaturated silane units maybe present in the functionalized olefin polymer preferably in an amountof from 0.1 to 50% by weight, more preferably from 0.1 to 10% by weightbased on the olefin polymer.

The composition may then be heated in the presence of water. In order toeffectively form the crosslinking with the aid of water, a catalyst mayalso be added. Examples of suitable catalysts include hydroxides and/oroxides of alkaline metals and alkaline earth metals, ammonia, amines,organic and inorganic acids, salts thereof, alkoxysilicons, and siliconhydrides. In some cases, the catalysts may be used directly without anyadditional treatment. The amount of the catalyst is usually from 0.001to 1 wt %, based on the weight of the functionalized olefin polymer. Atemperature at which the above-mentioned composition may be heated inthe presence of water is from about 50° C. to 200° C., preferably from80° C. to 120° C. Water may be in the form of steam, or the compositionmay be immersed into boiling water.

In the thus crosslinked olefin polymer, the ratio of the boilingxylene-insoluble component to this olefin polymer is preferably from 5to 100% by weight.

In another embodiment, the composition comprising a F-POA on whichhydrolyzable unsaturated silane is grafted can be blended with aphenolic antioxidant, a sulfide hydroperoxide decomposer and apolyvalent amine to prepare a water-crosslinkable composition.

Many kinds of phenolic antioxidants are known and commerciallyavailable. A preferred example of a phenolic antioxidant is asubstituted phenol such as 2,6-di-t-butylphenol in which a hydrogen atomat 2 and/or 6 position is substituted by an alkyl residue. Typicalexamples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol,2,4,6-tri-t-butylphenol, vitamin E,2-t-butyl-6-(3′-t-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenylacrylate, 2,2′-methylene-bis(4-methyl-6-t-butylphenyl),2,2′-methylene-bis(4-ethyl-6-t-butyl-phenol),2,2′-methylene-bis(6-cyclohexyl-4-methylphenol),1,6-hexanediol-bis([3-(3,5-di-t-butyl[4-hydroxyphenyl])]propionate andpentaerythrityl-tetrakis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)]propionate.

A preferable example of the sulfide hydroperoxide decomposer is an esterof a thioether, and typical examples of the commercially availablesulfide hydroperoxide decomposer include diesters of3,3′-thiodipropionic acid and higher alcohols such as lauryl alcohol,tridecyl alcohol and stearyl alcohol.

Examples of the polyvalent amine include melamine, its derivatives, ahydrazide compound such as oxalic acid-bis(benzylidenehydrazide) and atriazole compound such as 3-(N-salicyloyl)amino-1,2,4-triazole.

The amount of each of these additives to be added is such that theweight ratio of the additive to the F-POA is preferably 1/1000 to1/100000, more preferably 1/500 to 1/10000.

No particular restriction is put on the mixing manner of thefunctionalized olefin polymer and the stabilizer, which may be dry mixedutilizing, for example, a Henschel mixer, followed by melting and/orgranulation.

In another embodiment, phosphite additives are substantially absent fromthe blends of this invention. Preferably the phosphites are present atless than 1000 ppm, preferably less than 500 ppm, more preferably lessthan 100 ppm.

To the above-mentioned composition, there can be added a neutralizingagent such as calcium stearate, magnesium hydroxide, aluminum hydroxideor hydrotalcite, and a nucleating agent such as a salt of benzoic acid,sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl) phosphate and benzylsorbitol, and the like, in addition to the above-mentioned stabilizer.

Additives

In another embodiment, a composition comprising the polymer product ofthis invention may further comprise typical additives known in the artsuch as fillers, antioxidants, adjuvants, adhesion promoters, oils,and/or plasticizers. Preferred fillers include titanium dioxide, calciumcarbonate, barium sulfate, silica, silicon dioxide, carbon black, sand,glass beads, mineral aggregates, talc, clay and the like. Preferredantioxidants include phenolic antioxidants, such as Irganox 1010,Irganox, 1076 both available from Ciba-Geigy. Preferred oils includeparaffinic or napthenic oils such as Primol 352, or Primol 876 availablefrom ExxonMobil Chemical France, S.A. in Paris, France. Preferredplasticizers include polybutenes, such as Parapol 950 and Parapol 1300formerly available from ExxonMobil Chemical Company in Houston Tex.Other preferred additives include block, antiblock, pigments, processingaids, UV stabilizers, hindered amine light stabilizers, UV absorbers,neutralizers, lubricants, surfactants and/or nucleating agents may alsobe present in one or more than one layer in the films. Preferredadditives include silicon dioxide, titanium dioxide,polydimethylsiloxane, talc, dyes, wax, calcium sterate, carbon black,low molecular weight resins and glass beads. Preferred adhesionpromoters include polar acids, polyaminoamides (such as Versamid 115,125, 140, available from Henkel), urethanes (such as isocyanate/hydroxyterminated polyester systems, e.g. bonding agent TN/Mondur Cb-75 (Miles,Inc.), coupling agents, (such as silane esters (Z-6020 from DowCorning)), titanate esters (such as Kr-44 available from Kenrich),reactive acrylate monomers (such as sarbox SB-600 from Sartomer), metalacid salts (such as Saret 633 from Sartomer), polyphenylene oxide,oxidized polyolefins, acid modified polyolefins, and anhydride modifiedpolyolefins.

In another embodiment the composition may include less than 3 wt %anti-oxidant, less than 3 wt % flow improver, less than 10 wt % wax, andor less than 3 wt % crystallization aid.

Other optional components that may be combined with the adhesivecomposition as disclosed herein include plasticizers, and/or otheradditives such as oils, surfactants, fillers, color masterbatches, andthe like. Preferred plasticizers include mineral oils, polybutenes,phthalates and the like. Particularly preferred plasticizers includephthalates such as di-iso-undecyl phthalate (DIUP),di-iso-nonylphthalate (DINP), dioctylphthalates (DOP) and/or the like.Particularly preferred oils include aliphatic naphthenic oils.

Other optional components that may be combined with the polymer productof this invention are low molecular weight products such as wax, oil orlow Mn polymer, (low meaning below Mn of 5000, preferably below 4000,more preferably below 3000, even more preferably below 2500). Preferredwaxes include polar or non-polar waxes, functionalized waxes,polypropylene waxes, polyethylene waxes, and wax modifiers. Preferredwaxes include ESCOMER™ 101. Preferred functionalized waxes include thosemodified with an alcohol, an acid, a ketone, an anhydride and the like.Preferred examples include waxes modified by methyl ketone, maleicanhydride or maleic acid. Preferred oils include aliphatic napthenicoils, white oils, or the like. Preferred low Mn polymers includepolymers of lower alpha olefins such as propylene, butene, pentene,hexene and the like. A particularly preferred polymer includespolybutene having an Mn of less than 1000. An example of such a polymeris available under the trade name PARAPOL™ 950 from ExxonMobil ChemicalCompany. PARAPOL™ 950 is a liquid polybutene polymer having an Mn of 950and a kinematic viscosity of 220 cSt at 100° C., as measured by ASTM D445. In some embodiments the polar and non-polar waxes are used togetherin the same composition.

In some embodiments, however, wax may not be desired and may thus bepresent at less than 10 weight %, preferably less than 5 weight %, morepreferably less than 1 weight %, more preferably less than 0.5 weight %,based upon the weight of the composition.

In another embodiment the composition of this invention may have lessthan 30 weight % total of any combination of additives described above,preferably less than 25 weight %, preferably less than 20 weight %,preferably less than 15 weight %, preferably less than 10 weight %,preferably less than 5 weight %, based upon the total weight of F-POA,POA and other polymers present.

The composition of this invention or formulations thereof may then beapplied directly to a substrate or may be sprayed thereon. Thecomposition may be molten, or heated to a semisolid state prior orduring application. Spraying is defined to include atomizing, such asproducing an even dot pattern, spiral spraying such as NordsonControlled Fiberization or oscillating a stretched filament like may bedone in the ITW Dynafiber/Omega heads or Summit technology from Nordson.The compositions described herein may be applied using melt blowntechniques as well. Melt blown techniques are defined to include themethods described in U.S. Pat. No. 5,145,689 or any process where airstreams are used to break up filaments of the extrudate and then used todeposit the broken filaments on a substrate. In general, melt blowntechniques are processes that use air to spin hot melt adhesive fibersand convey them onto a substrate for bonding. Fibers sizes can easily becontrolled from 20-200 microns by changing the melt to air ratio. Few,preferably no, stray fibers are generated due to the inherent stabilityof adhesive melt blown applicators. Under UV light the bonding appearsas a regular, smooth, stretched dot pattern. Atomization is a processthat uses air to atomize hot melt adhesive into very small dots andconvey them onto a substrate for bonding.

Heat Stability

The compositions of the present invention preferably are heat stable, bywhich is meant that the Gardner color (as measured by ASTM D-1544-68) ofthe composition that has been heated to 180° C. for 48 hours, does notchange by more than 7 Gardner units when compared to the Gardner colorof the initial composition. Preferably, the Gardner color of thecomposition after heatingto 180° C. for 48 hours does not change by morethan 6, more preferably 5, still more preferably 4, still morepreferably 3, still more preferably 2, still more preferably 1 Gardnercolor unit, as compared to the initial composition prior to beingheated.

In a preferred embodiment, the F-POA is heat stable, by which is meantthat the Gardner color (as measured by ASTM D-1544-68) of the F-POA thathas been heated to 180° C. for 48 hours, does not change by more than 7Gardner units when compared to the Gardner color of the initial F-POA.Preferably, the Gardner color of the F-POA after heating to 180° C. for48 hours does not change by more than 6, more preferably 5, still morepreferably 4, still more preferably 3, still more preferably 2, stillmore preferably 1 Gardner color unit, as compared to the initial F-POAprior to being heated.

It has been discovered that free acid groups present in the compositionmay result in reduced heat stability. Accordingly, in a preferredembodiment, the amount of free acid groups present in the F-POA is lessthan about 1000 ppm, more preferably less than about 500 ppm, still morepreferably less than about 100 ppm, based on the total amount of F-POApresent.

In an embodiment, the composition may comprise F-POA in which at least aportion has been washed with an organic solvent, with an aqueoussolution, with an acidic solution, with a basic solution, or acombination thereof, prior to incorporation of the F-POA into the finalcomposition. Likewise, the entire composition may also be washed onceformed.

In a preferred embodiment, the acid value of the F-POA, after washingwith an aqueous solution, differs from the acid value of the F-POA priorto washing by less than about 10%, preferably by less than about 5%,more preferably by less than about 1% as determined by ASTM D-94-02

In a preferred embodiment, the F-POA comprises maleic anhydride, and theacid value of the F-POA, after washing with an aqueous solution, maydiffer from the acid value of the F-POA prior to washing by less thanabout 10%, preferably by less than about 5%, more preferably by lessthan about 1% as determined by ASTM D 94-02.

In another embodiment, the F-POA comprises an unsaturated groupcomprising a carbonyl group (preferably maleic anhydride), and peaksmeasured in the infrared spectrum of the composition attributable tofree acid content (e.g., —OH stretch, C═O stretch, and the like) arereduced in peak height by less than about 20%, preferably less thanabout 10%, more preferably less than about 5%, still more preferablyless than about 1%, as compared to the same peaks in an infra redspectrum of the composition measured essentially the same way after thecomposition has been devolatilized by heating at 180° C. for 30 minutes.

Lamination Melt Coating

The compositions of this invention may be used in any adhesiveapplication, including but not limited to, disposables, packaging,laminates, pressure sensitive adhesives, tapes labels, wood binding,paper binding, non-wovens, road marking, reflective coatings, and thelike.

In a preferred embodiment the adhesives of this invention can be usedfor disposable diaper and napkin chassis construction, elasticattachment in disposable goods converting, packaging, labeling,bookbinding, woodworking, and other assembly applications. Particularlypreferred applications include: baby diaper leg elastic, diaper frontaltape, diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

One or more of the embodiments of the compositions described above maybe applied to any substrate. Preferred substrates include wood, paper,cardboard, plastic, thermoplastic, rubber, metal, metal foil (such asaluminum foil and tin foil), metallized surfaces, cloth, non-wovens(particularly polypropylene spun bonded fibers or non-wovens), spunbonded fibers, cardboard, stone, plaster, glass (including silicon oxide(SiO_(x)) coatings applied by evaporating silicon oxide onto a filmsurface), foam, rock, ceramics, films, polymer foams (such aspolyurethane foam), substrates coated with inks, dyes, pigments, PVDCand the like or combinations thereof.

Additional preferred substrates include polyethylene, polypropylene,polyacrylates, acrylics, polyethylene terephthalate, or any of thepolymers listed above as suitable for blends.

Any of the above substrates, and/or the polymers of this invention, maybe corona discharge treated, flame treated, electron beam irradiated,gamma irradiated, microwaved, or silanized.

The adhesives produced herein, when coated in some fashion between twoadherends, preferably perform such that the materials are held togetherin a sufficient fashion compared to a standard specification or astandard adhesive similarly constructed. In so doing, the inventivecomposition may be utilized as a surface primer, as a tie layer, as anadhesion promoter, as a hot melt adhesive, as a compatiblizer, or thelike.

The compositions of this invention may be used in any adhesiveapplication described in WO 97/33921 in combination with the polymersdescribed therein or in place of the polymers described therein.

The compositions of this invention, alone or in combination with otherpolymers and or additives, may also be used to form hook and loopfasteners as described in WO 02/35956.

In a particularly preferred embodiment the compositions of thisinvention are used as adhesives in low temperature (less than 0° C.)applications.

In a particularly preferred embodiment the compositions of thisinvention are used as adhesives in high temperature (more than 40° C.)applications.

In a particularly preferred embodiment the compositions of thisinvention are used as adhesives in applications requiring both high andlow temperature performance (such as freezer to microwave applicationsor cardboard storage boxes for use in non-climate controlledwharehouses).

In a preferred embodiment this invention relates to:

-   1. A composition comprising a C3 to C40 olefin polymer olefin    polymer comprising at least 50 mol % of one or more C3 to C40    olefins, and where the olefin polymer has:    -   a) a Dot T-Peel of 1 Newton or more on Kraft paper;    -   b) an Mw of 10,000 to 100,000; and    -   c) a branching index (g′) of 0.98 or less measured at the Mz of        the polymer when the polymer has an Mw of 10,000 to 60,000, or

a branching index (g′) of 0.95 or less measured at the Mz of the polymerwhen the polymer has an Mw of 10,000 to 100,000; and where the C3 to C40olefin polymer comprises at least 0.001 weight % of an functional group.

-   2. The composition of paragraph 1, wherein the C3 to C40 olefin    polymer, prior to functionalization, has:

a) a Dot T-Peel of 1 Newton or more on Kraft paper;

b) a branching index (g′) of 0.98 or less measured at the Mz of thepolymer;

c) a Mw of 10,000 to 60,000; and

d) a heat of fusion of 1 to 50 J/g.

-   3. The composition of paragraph 1 or 2, where the C3 to C40 olefin    polymer, prior to functionalization, is a homopolypropylene or a    copolymer of propylene and up to 5 mole % ethylene having:

a) an isotactic run length of 1 to 30,

b) a percent of r dyad of greater than 20%, and

c) a heat of fusion of between 1 and 70 J/g.

-   4. The composition of any of paragraphs 1-3, wherein the C3 to C40    olefin polymer, prior to functionalization, comprises propylene and    less than 15 mole % of ethylene.-   5. The composition of any of paragraphs 1-4, wherein the C3 to C40    olefin polymer, prior to functionalization, has a melt viscosity of    7000 mPa·sec or less at 190° C.-   6. The composition of any of paragraphs 1-5, wherein the C3 to C40    olefin polymer, prior to functionalization, has a melt viscosity of    5000 mPa·sec or less at 190° C.-   7. The composition of any of paragraphs 1-6, wherein the C3 to C40    olefin polymer, prior to functionalization, has a melt viscosity of    between 250 and 6000 mPa·sec at 190° C.-   8. The composition of any of paragraphs 1-7, wherein the C3 to C40    olefin polymer, prior to functionalization, has a melt viscosity of    between 500 and 3000 mPa·sec at 190° C.-   9. The composition of any of paragraphs 1-8, wherein the C3 to C40    olefin polymer, prior to functionalization, has a Tg of 0° C. or    less.-   10. The composition of any of paragraphs 1-9, wherein the C3 to C40    olefin polymer, prior to functionalization, has a Tg of −10° C. or    less.-   11. The composition of any of paragraphs 1-10, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mw of 10,000 to    75,000 and a branching index of 0.6 or less.-   12. The composition of any of paragraphs 1-11, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mw of 10,000 to    50,000 and a branching index of 0.7 or less.-   13. The composition of any of paragraphs 1-12, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mw of 10,000 to    30,000 and a branching index of 0.98 or less.-   14. The composition of any of paragraphs 1-13, wherein the C3 to C40    olefin polymer, prior to functionalization, has a branching index    (g′) of 0.90 or less measured at the Mz of the polymer.-   15. The composition of any of paragraphs 1-14, wherein the SEC graph    of the C3 to C40 olefin polymer, prior to functionalization, is bi-    or multi-modal.-   16. The composition of any of paragraphs 1-15, wherein the C3 to C40    olefin polymer, prior to functionalization, has an amorphous content    of at least 50%.-   17. The composition of any of paragraphs 1-16, wherein the C3 to C40    olefin polymer, prior to functionalization, has

a) a peak melting point between 60 and 190° C.;

b) a heat of fusion of 0 to 70 J/g; and

c) a melt viscosity of 8000 mPa·sec or less at 190° C.

-   18. The composition of any of paragraphs 1-17, wherein the C3 to C40    olefin polymer, prior to functionalization, has:

a) a Tg of −10° C. or less;

b) a melt viscosity between 2000 and 6000 mPa·sec;

c) a molecular weight distribution (Mw/Mn) of at least 5; and

d) a bi- or multi-modal SEC graph of the polymer.

-   19. The composition of any of paragraphs 1-18, wherein the C3 to C40    olefin polymer, prior to functionalization, has a crystallinity of    at least 5%.-   20. The composition of any of paragraphs 1-19, wherein the C3 to C40    olefin polymer, prior to functionalization, has 20 wt. % or more of    hexane room temperature soluble fraction and 50 wt % or less of    Soxhlet heptane insolubles.-   21. The composition of any of paragraphs 1-20, wherein the C3 to C40    olefin polymer, prior to functionalization, comprises less than 3.0    mole % ethylene.-   22. The composition of any of paragraphs 1-21, wherein the C3 to C40    olefin polymer, prior to functionalization, comprises less than 1.0    mole % ethylene.-   23. A composition comprising the composition of any of paragraphs    1-22 and a functionalized wax.-   24. A composition comprising the composition of any of paragraphs    1-23 and a wax.-   25. A composition comprising the composition of any of paragraphs    1-24 and a hydrocarbon resin.-   26. The composition of any of paragraphs 1-25 wherein the functional    group is present at 0.005 to 50 weight % of the C3 to C40 olefin    polymer.-   27. The composition of any of paragraphs 1-26 wherein the functional    group is present at 1 to 20 weight % of the C3 to C40 olefin    polymer.-   28. The composition of any of paragraphs 1-27 wherein the    unsaturated group comprises maleic acid and or maleic anhydride.-   29. The composition of any of paragraphs 1-28, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mz/Mn of 2 to    200.-   30. The composition of any of paragraphs 1-29, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mz of 15,000 to    500,000.-   31. The composition of any of paragraphs 1-30 wherein the    composition has a SAFT of 50 to 150° C.-   32. The composition of any of paragraphs 1-31, wherein the    composition has a Shore A hardness of 95 or less.-   33. The composition of any of paragraphs 1-32, wherein the    composition has a set time of 5 seconds or less.-   34. The composition of any of paragraphs 1-33, wherein the C3 to C40    olefin polymer, prior to functionalization, has an Mw/Mn of 2 to 75.-   35. The composition of any of paragraphs 1-34, wherein the C3 to C40    olefin polymer is functionalized with an unsaturated carboxylic    acid, an ester of an unsaturated carboxylic acid, an acid anhydride,    a di-ester, a salt of an unsaturated carboxylic acid, an unsaturated    amide, an unsaturated imide, an aromatic vinyl compound, a    hydrolyzable unsaturated silane compound, an unsaturated halogenated    hydrocarbon, or a combination thereof-   36. The composition of any of paragraphs 1-35, wherein the C3 to C40    olefin polymer is functionalized with one or more of maleic    anhydride, citraconic anhydride, 2-methyl maleic anhydride,    2-chloromaleic anhydride, 2,3-dimethylmaleic anhydride,    bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride,    4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid,    methacrylic acid, maleic acid, fumaric acid, itaconic acid,    citraconic acid, mesaconic acid, crotonic acid,    bicyclo(2.2.2)oct-5-ene-2,3-dicarboxylic acid anhydride,    1,2,3,4,5,&g, lo-octahydronaphthalene-2,3-dicarboxylic acid    anhydride, 2-oxa-1,3-diketospiro(4.4)non-7-ene,    bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride,    maleopimaric acid, tetrahydrophtalic anhydride,    norborn-5-ene-2,3-dicarboxylic acid anhydride, nadic anhydride,    methyl nadic anhydride, himic anhydride, methyl himic anhydride,    x-methyl-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid anhydride    (XMNA), methyl acrylate, ethyl acrylate, butyl acrylate, methyl    methacrylate, ethyl methacrylate, butyl methacrylate,    vinyltrichlorosilane, vinyltris(beta-methoxyethoxy)silane,    vinyltriethoxysilane, vinyltrimethoxysilane,    gamma-methacryloxypropyltrimethoxysilane monovinylsilane,    monoallylsilane, vinyl chloride, or vinylidene chloride.-   37. The composition of any of paragraphs 1-36, wherein the    functional group is maleic anhydride.-   38. The composition of any of paragraphs 1-37, wherein the    composition further comprises another polymer.-   39. The composition of paragraph 38, wherein the polymer comprises    an olefin homopolymer or copolymer that is not functionalized.-   40. The composition of paragraph 38 or 39, wherein the polymer    comprises an olefin homopolymer or copolymer that comprises a    different functional group or groups.-   41. The composition of any of paragraphs 38-40, wherein the polymer    comprises a functionalized C3 to C40 olefin polymer that comprises a    different amount of the same functionalized group.-   42. The composition of any of paragraphs 38-41, wherein the polymer    comprises an alpha-olefin homopolymer comprising ethylene, C4 to C20    alpha olefins, or a combination thereof-   43. The composition of any of paragraphs 38-42, wherein the polymer    is selected from the group consisting of ethylene propylene rubber,    ethylene propylene diene monomer rubber, styrenic block copolymer    rubber, butyl rubber, halobutyl rubber, copolymers of isobutylene    and para-alkylstyrene, halogenated copolymers of isobutylene and    para-alkylstyrene, natural rubber, polyisoprene, copolymers of    butadiene with acrylonitrile, polychloroprene, alkyl acrylate    rubber, chlorinated isoprene rubber, acrylonitrile chlorinated    isoprene rubber, polybutadiene rubber or a combination thereof-   44. The composition of any of paragraphs 38-43, wherein the polymer    is selected from the group consisting of isotactic polypropylene,    highly isotactic polypropylene, syndiotactic polypropylene, random    copolymer of propylene and ethylene and/or butene and/or hexene,    polybutene, ethylene vinyl acetate, low density polyethylene    (density 0.915 to less than 0.935 g/cm³) linear low density    polyethylene, ultra low density polyethylene (density 0.86 to less    than 0.90 g/cm³), very low density polyethylene (density 0.90 to    less than 0.915 g/cm³), medium density polyethylene (density 0.935    to less than 0.945 g/cm³), high density polyethylene (density 0.945    to 0.98 g/cm³), ethylene vinyl acetate, ethylene methyl acrylate,    copolymers of acrylic acid, polymethylmethacrylate,    polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins,    polyamides, polycarbonates, PET resins, crosslinked polyethylene,    copolymers of ethylene and vinyl alcohol (EVOH), polymers of    aromatic monomers such as polystyrene, poly-1 esters, polyacetal,    polyvinylidine fluoride, polyethylene glycols andor polyisobutylene.-   45. The composition of any of paragraphs 38-44, wherein the polymer    is selected from the group consisting of metallocene polyethylenes    or metallocene polypropylenes.-   46. The composition of any of paragraphs 1-45 wherein the    composition further comprises a non-functionalized C3 to C40 olefin    polymer comprising at least 50 mol % of one or more C3 to C40    olefins, and where the olefin polymer has:    -   a) a Dot T-Peel of 1 Newton or more on Kraft paper;    -   b) an Mw of 10,000 to 100,000; and    -   c) a branching index (g′) of 0.98 or less measured at the Mz of        the polymer when the polymer has an Mw of 10,000 to 60,000, or

a branching index (g′) of 0.95 or less measured at the Mz of the polymerwhen the polymer has an Mw of 10,000 to 100,000.

-   47. The composition of paragraph 46, wherein the non-functionalized    C3 to C40 olefin polymer has:    -   a) a Dot T-Peel of 1 Newton or more on Kraft paper;    -   b) a branching index (g′) of 0.98 or less measured at the Mz of        the polymer;    -   c) a Mw of 10,000 to 60,000; and    -   d) a heat of fusion of 1 to 50 J/g.-   48. The composition of paragraph 46, where the non-functionalized C3    to C40 olefin polymer is a homopolypropylene or a copolymer of    propylene and up to 5 mole % ethylene having:

a) an isotactic run length of 1 to 30,

b) a percent of r dyad of greater than 20%, and

c) a heat of fusion of between 1 and 70 J/g.

-   49. The composition of any of paragraphs 46-48, wherein the    non-functionalized C3 to C40 olefin polymer has a melt viscosity of    5000 mPa·sec or less at 190° C.-   50. The composition of any of paragraphs 46-49, wherein the    non-functionalized C3 to C40 olefin polymer has an amorphous content    of at least 50%.-   51. The composition of any of paragraphs 46-50, wherein the    non-functionalized C3 to C40 olefin polymer has a crystallinity of    at least 5%.-   52. The composition of any of paragraphs 1-51, further comprising    about 0.1 to about 50 wt % of a tackifier, a filler, an antioxidant,    an adjuvant, an adhesion promoter, an oil, a plasticizer, a block,    an antiblock, a pigment, a processing aid, a UV stabilizer, a    neutralizer, a lubricant, a surfactant, a nucleating a coupling    agent, a color master batch, a polymer having a Mn below 5000, a    polar wax, a non-polar wax, a functionalized wax, a polypropylene    wax, a polyethylene wax, a wax modifier, an elastomer, an impact    copolymer, an ester polymer, a crosslinking agent, or a combination    thereof-   53. The composition of any of paragraphs 1-52, wherein the Gardner    color of the composition that has been heat aged at 180° C. for 48    hours does not change by more than 7 Gardner units as compared to    the Gardner color of the composition prior to being heat aged.-   54. The composition of any of paragraphs 1-53, wherein the Gardner    color of the composition that has been heat aged at 180° C. for 48    hours does not change by more than 4 Gardner units as compared to    the Gardner color of the composition prior to being heat aged.-   55. The composition of any of paragraphs 1-54, wherein the amount of    free acid groups present in component 2 is less than about 1000    parts per million, based on the total amount of functionalized C3 to    C40 olefin polymer present.-   56. The composition of any of paragraphs 1-55, which is essentially    free from phosphites.-   57. The composition of any of paragraphs 1-56, the C3 to C40 olefin    polymer comprising at least 0.001 to 50 weight % functional group    has been washed with an organic solvent, with an aqueous solution,    with an acidic solution, with a basic solution, or a combination    thereof-   58. The composition of any of paragraphs 1-57, wherein the    functional group comprises maleic anhydride and the at least a    portion of the polymer has been washed with a basic solution.-   59. The composition of paragraph 58, wherein an acid value of the    polymer, after washing with the basic solution differs from the acid    value of the polymer prior to the washing by less than about 10%.-   60. The composition of paragraph 58 or 59, wherein one or more peaks    measured in an infrared spectrum of the composition attributable to    free acid content are reduced in peak height by less than about 20%    compared to the same peaks in an infra red spectrum of the    composition measured essentially the same way after the composition    has been devolatilized by heating at 180° C. for 30 minutes.-   61. A process of making the composition of any of paragraphs 1-60,    comprising the steps of:    -   1) combining monomer, optional solvent, catalyst and activator        in a reactor system;    -   2) withdrawing olefin polymer solution from the reactor system,        where the polymer comprises at least 50 mol % of one or more C3        to C40 olefins and has:        -   a) a Dot T-Peel of 1 Newton or more on Kraft paper;        -   b) an Mw of 10,000 to 100,000; and        -   c) a branching index (g′) of 0.98 or less measured at the Mz            of the polymer when the polymer has an Mw of 10,000 to            60,000, or        -   a branching index (g′) of 0.95 or less measured at the Mz of            the polymer when the polymer has an Mw of 10,000 to 100,000;    -   3) removing at least 10% solvent, if present, from the olefin        polymer solution;    -   4) quenching the reaction;    -   5) devolatilizing the olefin polymer solution to form molten        olefin polymer;    -   6) combining at least a portion of the molten olefin polymer        with an functional group in the presence of a radical initiator        at a temperature, and for a period of time sufficient to produce        molten functionalized olefin polymer;    -   7) combining the molten functionalized polymer, the olefin        polymer, and optionally one or more additives in a mixer and        mixing to produce a composition;    -   8) removing the composition from the mixer, and    -   9) pelletizing or drumming the composition.-   62. A surface primer comprising the composition of any of paragraphs    1-61.-   63. A tie layer comprising the composition of any of paragraphs    1-62.-   64. An adhesion promoter comprising the composition of any of    paragraphs 1-63.-   65. A hot melt adhesive comprising the composition of any of    paragraphs 1-64.-   66. A compatiblizer comprising the composition of any of paragraphs    1-65.

Examples Analytical Testing

Molecular weights (number average molecular weight (Mn), weight averagemolecular weight (Mw), and z-average molecular weight (Mz)) weredetermined using a Waters 150 Size Exclusion Chromatograph (SEC)equipped with a differential refractive index detector (DRI), an onlinelow angle light scattering (LALLS) detector and a viscometer (VIS). Thedetails of the detector calibrations have been described elsewhere [SeeT. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules,Volume 34, Number 19, 6812-6820, (2001)].

The SEC with three Polymer Laboratories PLgel 10 mm Mixed-B columns, anominal flow rate 0.5 cm³/min, and a nominal injection volume 300microliters was common to both detector configurations. The varioustransfer lines, columns and differential refractometer (the DRIdetector, used mainly to determine eluting solution concentrations) werecontained in an oven maintained at 135° C.

The LALLS detector used was a model 2040 dual-angle light scatteringphotometer (Precision Detector Inc.). Its flow cell, located in the SECoven, uses a 690 nm diode laser light source and collects scatteredlight at 15° and 90°. The 15° output was used herein. The signalgenerated was sent to a data acquisition board (National Instruments)that accumulates readings at a rate of 16 per second. The lowest fourreadings were averaged, and the proportional signal was sent to theSEC-LALLS-VIS computer. The LALLS detector was placed after the SECcolumns, and before the viscometer.

The viscometer was a high temperature Model 150R (Viscotek Corporation)having four capillaries arranged in a Wheatstone bridge configurationwith two pressure transducers. One transducer measures the totalpressure drop across the detector, and the other, positioned between thetwo sides of the bridge, measures a differential pressure. The specificviscosity for the solution flowing through the viscometer was calculatedfrom these outputs. The viscometer was inside the SEC oven, positionedafter the LALLS detector but before the DRI detector.

Solvent for the SEC experiment was prepared by adding 6 grams ofbutylated hydroxy toluene (BHT) as an antioxidant to a 4 liter bottle of1,2,4 Trichlorobenzene (TCB) (Aldrich Reagent grade) and waiting for theBHT to solubilize. The TCB mixture was then filtered through a 0.7micron glass pre-filter and subsequently through a 0.1 micron Teflonfilter. There was an additional online 0.7 micron glass pre-filter/0.22micron Teflon filter assembly between the high pressure pump and SECcolumns. The TCB was then degassed with an online degasser (Phenomenex,Model DG-4000) before entering the SEC.

Sample solutions were prepared by placing the dry polymer sample in aglass container, adding the desired amount of TCB, then heating themixture at 160° C. with continuous agitation for about 2 hours. Allquantities were measured gravimetrically. The TCB densities used toexpress the polymer concentration in mass/volume units were 1.463 g/mlat room temperature and 1.324 g/ml at 135° C. The injectionconcentration ranged from 1.0 to 2.0 mg/ml, with lower concentrationsbeing used for higher molecular weight samples.

Prior to running each sample the DRI detector and the injector werepurged. Flow rate in the apparatus was then increased to 0.5 ml/minute,and the DRI was allowed to stabilize for 8-9 hours before injecting thefirst sample. The argon ion laser was turned on 1 to 1.5 hours beforerunning samples by running the laser in idle mode for 20-30 minutes andthen switching to full power in light regulation mode.

The branching index was measured using SEC with an on-line viscometer(SEC-VIS) and are reported as g′ at each molecular weight in the SECtrace. The branching index g′ is defined as:

$g^{\prime} = \frac{\eta_{b}}{\eta_{l}}$

where η_(b) is the intrinsic viscosity of the branched polymer and η_(I)is the intrinsic viscosity of a linear polymer of the sameviscosity-averaged molecular weight (M_(v)) as the branched polymer.η_(I)=KM_(v) ^(α), K and α were measured values for linear polymers andshould be obtained on the same SEC-DRI-LS-VIS instrument as the one usedfor branching index measurement. For polypropylene samples presented inthis invention, K=0.0002288 and α=0.705 were used. The SEC-DRI-LS-VISmethod obviates the need to correct for polydispersities, since theintrinsic viscosity and the molecular weight were measured at individualelution volumes, which arguably contain narrowly dispersed polymer.Linear polymers selected as standards for comparison were of the sameviscosity average molecular weight, monomer content and compositiondistribution. Linear character for polymer containing C2 to C10 monomersis confirmed by Carbon-13 NMR according to Randall (Rev. Macromol. Chem.Phys., C29 (2&3), p. 285-297). Linear character for C11 and abovemonomers was confirmed by GPC analysis using a MALLS detector. Forexample, for a copolymer of propylene, the NMR should not indicatebranching greater than that of the co-monomer (i.e. if the comonomer isbutene, branches of greater than two carbons should not be present). Fora homopolymer of propylene, the GPC should not show branches of morethan one carbon atom. When a linear standard was desired for a polymerwhere the comonomer is C9 or more, protocols described by T. Sun, P.Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34,Number 19, 6812-6820, (2001) were used in determining standards. In thecase of syndiotactic polymers, the standard was selected to have acomparable amount of syndiotacticity as measured by Carbon 13 NMR.

Peak melting point (Tm), peak crystallization temperature (Tc), heat offusion and crystallinity were determined using ASTM E 794-85.Differential scanning calorimetric (DSC) data was obtained using a TAInstruments model 2920. e.g., samples weighing approximately 7-10 mgwere sealed in aluminum sample pans. The DSC data was recorded by firstcooling the sample to −50° C. and then gradually heating it to 200° C.at a rate of 10° C./minute. The sample was kept at 200° C. for 5 minutesbefore a second cooling-heating cycle was applied. Both the first andsecond cycle thermal events were recorded. Areas under the curves weremeasured and used to determine the heat of fusion and the degree ofcrystallinity. The percent crystallinity is calculated using theformula, [area under the curve (Joules/gram)/B (Joules/gram)]*100, whereB is the heat of fusion for the homopolymer of the major monomercomponent. These values for B were obtained from the Polymer Handbook,Fourth Edition, published by John Wiley and Sons, New York 1999. A valueof 189 J/g (B) was used as the heat of fusion for 100% crystallinepolypropylene. For polymers displaying multiple melting orcrystallization peaks, the highest melting peak was taken as peakmelting point, and the highest crystallization peak was taken as peakcrystallization temperature.

The glass transition temperature (Tg) was measured by ASTM E 1356 usinga TA Instruments model 2920.

Melt Viscosity was determined according to ASTM D-3236, which is alsoreferred to herein as “viscosity” and/or “Brookfield viscosity”. Meltviscosity profiles were measured at a temperature from 120° C. to 190°C. using a Brookfield Thermosel viscometer and a number 27 spindleunless otherwise noted.

Adhesive Testing

The samples were prepared consistent with testing of adhesives, inparticular, hot melt adhesives, by using the olefin polymers or blendingthe olefin polymers, functionalized olefin polymers, additives,tackifier, wax, antioxidant, and other ingredients or components undermixing at elevated temperatures to form fluid melt. The mixingtemperature varied from about 130 to about 190° C. Adhesive testspecimens were created by bonding the substrates together with a portion(e.g., a dot) of molten adhesive and compressing the bond with a500-gram weight until cooled to room temperature (i.e., about 25° C.).The dot size was controlled by the adhesive volume such that in mostcases the compressed disk which formed gave a uniform circle just insidethe dimensions of the substrates. Once a construct has been produced, itwas be subjected to various insults in order to assess the effectivenessof the bond.

Once a bond fails to a paper substrate the effectiveness of the bond wasquantified by estimating the area of the adhesive dot that retainedpaper fibers as the construct failed along the bond line. This estimateis referred to herein as the percent substrate fiber tear. An example ofgood fiber, after conditioning a sample for 15 hours at −12° C. andattempting to destroy the bond, would be an estimate of 80-100%substrate fiber tear. It is likely that 0% substrate fiber tear underthose conditions would signal a loss of adhesion.

Substrate fiber tear: The specimens were prepared using the sameprocedure as that described above. For low temperature fiber tear test,the bond specimens were placed in a freezer or refrigerator to obtainthe desired test temperature. For substrate fiber tear at roomtemperature, the specimens were aged at ambient conditions. The bondswere separated by hand and a determination made as to the type offailure observed. The amount of substrate fiber tear is expressed hereinas a percentage.

Dot T-Peel was determined according to ASTM D 1876, except that thespecimen was produced by combining two 1 inch by 3 inch (2.54 cm×7.62cm) substrate cut outs with a dot of adhesive with a volume that, whencompressed under a 500-gram weight occupied about 1 square inch of area(1 inch=2.54 cm). Once all the specimens were made, each were pulledapart in a side by side testing arrangement at a rate of 2 inches perminute by a machine that records the destructive force of the insultbeing applied. The maximum force achieved for each sample tested wasrecorded and averaged, thus producing the average maximum force which isreported as the Dot T-Peel.

Peel Strength (modified ASTM D1876): Substrates (1×3 inches (25×76 mm))were heat sealed with adhesive film (5 mils (130 μm) thickness) at 135°C. for 1 to 2 seconds and 40 psi (0.28 MPa) pressure. Bond specimenswere peeled back in a tensile tester at a constant crosshead speed of 2in/min (51 mm/min). The average force required to peel the bond (5specimens) apart was recorded.

Set time is defined for use herein as the time it takes for a compressedadhesive substrate construct to fasten together with enough adhesion soas to give substrate fiber tear when pulled apart, and thus the bond issufficiently strong to remove the compression. The bond will likelystill strengthen upon further cooling, however, it no longer requirescompression. These set times were measured by placing a molten dot ofadhesive on to a file folder substrate taped to a flat table. A filefolder tab (1 inch by 3 inch (2.5 cm×7.6 cm)) was placed upon the dot 3seconds later and compressed with a 500 gram weight. The weight wasallowed to sit for about 0.5 to about 10 seconds. The construct thusformed was pulled apart to check for a bonding level sufficient toproduce substrate fiber tear. The set time was recorded as the minimumtime required for this bonding to occur. Standards of commerciallyavailable adhesives were used to calibrate this process.

SAFT (modified D4498) measures the ability of a bond to withstand anelevated temperature rising at 10° F. (5.5° C.)/15 min., under aconstant force that pulls the bond in the shear mode. Bonds were formedin the manner described above on Kraft paper (1 inch by 3 inch (2.5cm×7.6 cm)). The test specimens were suspended vertically in an oven atroom temperature with a 500-gram load attached to the bottom. Thetemperatures at which the weight fell was recorded (when the occasionalsample reached temperatures above the oven capacity>265° F. (129° C.) itwas terminated and averaged in with the other samples at terminationtemperature).

Shore A hardness was measured according to ASTM D 2240. An air cooleddot of adhesive was subjected to the needle and the deflection wasrecorded from the scale.

Sample Preparation and Description

Two POA homopolypropylenes were produced according to the generalprocedures described in U.S. Ser. No. 10/868,951, filed Oct. 15, 2003.The catalysts used were di(p-triethylsilylphenyl)methylene(cyclopentadienyl)(3,8-di-t-butylfluorenyl)hafnium dimethyl andrac-dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconium dimethyl theactivator used wasN,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate. Thepolymerization was run at 131° C. in hexane.) The polymer properties arelisted in Table A.

TABLE A Viscosity Tc Tm Mn Mw Mz 190° C., g′ @ (° (° Hf (kg/mol (kg/mol(kg/mol (cps) Mz C.) C.) (J/g) POA 19,600 41,100 76,000 1600 0.82 78 13228.7 11 POA 20,700 40,600 72,500 1522 0.82 69 132 29.5 12

Two blends of POA 12 were made. One where the POA-12 was functionalizedwith maleic anhydride and one without.

POA-12-g-MA

POA-12 was functionalized by dissolving 120 g of POA-12 polymer intoluene (polymer concentration is about 20 wt. %) to which 15 wt. %(based on polymer) of maleic anhydride was added. 2.5 wt % of2,5-dimethyl-2,5-di(t-butylperoxyl)hexane was added and the reaction washeated to 139° C. and allowed to react for 4 hours. The method describedby M. Sclavons et al. (Polymer, 41 (2000), page 1989) was used todetermine the MA content of the maleated polymer. Briefly, about 0.5gram of polymer was dissolved in 150 ml of toluene at the boilingtemperature.

A potentiometric titration with tetra-butylammonium hydroxide usingbromothymol blue as the color indicator was performed on the heatedsolution in which the polymer did not precipitate during the titration.The POA-12-g-MA was found to contain 1.41 weight % MA. Adhesion testingwas then conducted on the POA-12-, POA-11, and POA-12-g-MA blended withother components. The data are as follows:

Example 1 Example 2 Example 3 POA-12 (wt %) 74.3 79.3 POA-11 (wt %) 81.6POA-12-g-MA (wt %) 5 Escorez 5690 (wt. %) 10 10 9.0 C80 Wax (wt. %) 1010 8.7 Irganox 1010 (wt. %) 0.7 0.7 0.7 Set time (sec) 3.5 3 3.5 Shore Ahardness 81/71 83/63 84/64 Percent of fiber tear on Inland 94 96 99paperboard @ 25° C. Percent of fiber tear on Inland 43 0 0 paperboard @−10° C. Percent of fiber tear on Inland 68 13 0 paperboard @ −30° C.

Escorez 5690 is a hydrogenated aromatic modified resin produced fromdicyclopentadiene feedstock, exhibiting a ring and ball softening pointof 130° C. available from ExxonMobil in Houston, Tex.

C80 wax is Paraflint C80 propylene wax—which is a Fischer Tropschfractionated wax, available from Moore and Munger.

As the data clearly shows, the inventive adhesive formulationdramatically improved the adhesion at −10° C. and −30° C.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent from the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly, it is not intended thatthe invention be limited thereby.

We claim: 1-16. (canceled)
 17. A composition comprising a functionalizedC3 to C40 olefin polymer; and an additional non-functionalized polymercomprising at least 70% propylene; wherein the additionalnon-functionalized polymer has at least two molecular weights fractionspresent at greater than 20 weight % each based upon the weight of thepolymer as measured by Gel Permeation Chromatography; and wherein thenon-functionalized polymer has a Dot T-Peel of 1 Newton or more on Kraftpaper and an Mw of 10,000 to 100,000.
 18. The composition of claim 17,wherein the functionalized C3 to C40 olefin polymer is present in thecomposition in the range of 2 to 20 weight %.
 19. The composition ofclaim 17, wherein the functionalized C3 to C40 olefin comprises at least0.0001 weight % of a functional group.
 20. The composition of claim 20,wherein the functional group is maleic anhydride.
 21. The composition ofclaim 17, wherein the functionalized C3 to C40 olefin polymer has a Mwof 10,0000 to 100,000.
 22. The composition of claim 17, wherein thenon-functionalized polymer has a heat of fusion between 20 and 50 J/g.23. The composition of claim 17, wherein the non-functionalized polymercomprises at least 80% propylene.
 24. The composition of claim 17,wherein the non-functionalized polymer comprises a branching index (g′)of 0.98 or less measured at the Mz of the polymer when the polymer hasan Mw of 10,000 to 60,000, or a branching index (g′) of 0.95 or lessmeasured at the Mz of the polymer when the polymer has an Mw of 10,000to 100,000.
 25. The composition of claim 17, wherein thenon-functionalized C3 to C40 olefin polymer has a melt viscosity of 7000mPa·sec or less at 190° C.
 26. The composition of claim 17, wherein thenon-functionalized C3 to C40 olefin polymer has a Tg of 0° C. or less.27. The composition of claim 17, wherein the non-functionalized polymercomprises 5 mole % ethylene or less.